U.S. patent number 8,389,452 [Application Number 12/762,096] was granted by the patent office on 2013-03-05 for polymeric compositions useful as rheology modifiers and methods for making such compositions.
This patent grant is currently assigned to ExxonMobil Chemical Patents Inc.. The grantee listed for this patent is Jo Ann Marie Canich, Sudhin Datta, Liehpao Oscar Farng, Rainer Kolb, Vera Minak-Bernero, Eric B. Sirota, Thomas Tungshi Sun, Mun Fu Tse, Manika Varma-Nair. Invention is credited to Jo Ann Marie Canich, Sudhin Datta, Liehpao Oscar Farng, Rainer Kolb, Vera Minak-Bernero, Eric B. Sirota, Thomas Tungshi Sun, Mun Fu Tse, Manika Varma-Nair.
United States Patent |
8,389,452 |
Datta , et al. |
March 5, 2013 |
**Please see images for:
( Certificate of Correction ) ** |
Polymeric compositions useful as rheology modifiers and methods for
making such compositions
Abstract
Disclosed are rheology modifiers comprising compositionally
disperse polymeric compositions and/or crystallinity disperse
polymeric compositions that may be useful in modifying the
rheological properties of lubrication fluids, and methods for
making such compositions. The compositionally disperse polymeric
composition are formed from at least two discrete compositions of
ethylene copolymers. The crystallinity disperse polymeric
composition are formed from ethylene copolymers having at least two
discrete values of residual crystallinity.
Inventors: |
Datta; Sudhin (Houston, TX),
Canich; Jo Ann Marie (Houston, TX), Farng; Liehpao Oscar
(Lawrenceville, NJ), Kolb; Rainer (Kingwood, TX),
Minak-Bernero; Vera (Bridgewater, NJ), Sirota; Eric B.
(Flemington, NJ), Sun; Thomas Tungshi (Clinton, NJ), Tse;
Mun Fu (Seabrook, TX), Varma-Nair; Manika (Warren,
NJ) |
Applicant: |
Name |
City |
State |
Country |
Type |
Datta; Sudhin
Canich; Jo Ann Marie
Farng; Liehpao Oscar
Kolb; Rainer
Minak-Bernero; Vera
Sirota; Eric B.
Sun; Thomas Tungshi
Tse; Mun Fu
Varma-Nair; Manika |
Houston
Houston
Lawrenceville
Kingwood
Bridgewater
Flemington
Clinton
Seabrook
Warren |
TX
TX
NJ
TX
NJ
NJ
NJ
TX
NJ |
US
US
US
US
US
US
US
US
US |
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Assignee: |
ExxonMobil Chemical Patents
Inc. (Houston, TX)
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Family
ID: |
42992685 |
Appl.
No.: |
12/762,096 |
Filed: |
April 16, 2010 |
Prior Publication Data
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Document
Identifier |
Publication Date |
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US 20100273693 A1 |
Oct 28, 2010 |
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Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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61173528 |
Apr 28, 2009 |
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61173501 |
Apr 28, 2009 |
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61299816 |
Jan 29, 2010 |
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61297621 |
Jan 22, 2010 |
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Current U.S.
Class: |
508/591;
525/70 |
Current CPC
Class: |
C08L
23/16 (20130101); C10M 143/04 (20130101); C10M
143/08 (20130101); C10M 143/00 (20130101); C08F
210/16 (20130101); C10M 143/06 (20130101); C08F
210/06 (20130101); C08F 210/06 (20130101); C08F
4/65927 (20130101); C10N 2030/02 (20130101); C10M
2205/022 (20130101); C10N 2020/02 (20130101); C10N
2020/019 (20200501); C10N 2020/04 (20130101); C08F
4/65908 (20130101); C10N 2030/68 (20200501); C10N
2020/06 (20130101); C10N 2020/01 (20200501); C10M
2205/022 (20130101); C10M 2205/024 (20130101); C10M
2205/022 (20130101); C10M 2209/062 (20130101); C08F
210/16 (20130101); C08F 210/06 (20130101); C08F
2500/12 (20130101); C08F 2500/03 (20130101); C10M
2205/022 (20130101); C10M 2205/026 (20130101); C10M
2205/022 (20130101); C10M 2205/028 (20130101) |
Current International
Class: |
C10L
1/16 (20060101); C08G 63/48 (20060101) |
Field of
Search: |
;508/591 ;525/70 |
References Cited
[Referenced By]
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WO |
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WO 2009/012153 |
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Jan 2009 |
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WO |
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WO 2010/126721 |
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Nov 2010 |
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WO |
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|
Primary Examiner: Griffin; Walter D
Assistant Examiner: Campanell; Francis C
Parent Case Text
US PRIORITY
This application claims the priority to and the benefit from U.S.
Ser. No. 61/173,528, filed on Apr. 28, 2009, U.S. Ser. No.
61/173,501, filed on Apr. 28, 2009, and U.S. Ser. No. 12/569,009,
filed on Sep. 29, 2009, all of which are incorporated herein by
reference in their entirety.
CROSS REFERENCE TO RELATED APPLICATIONS
This application is related to U.S. Ser. No. 61/299,816, filed on
Jan. 29, 2010, and U.S. Ser. No. 61/297,621, filed on Jan. 22,
2010, which are herein incorporated by reference in their entirety.
Claims
What is claimed is:
1. A polymeric composition comprising: (a) a first ethylene
copolymer having: i. an E.sub.A in the range from greater than or
equal to 35 to less than or equal to 60; ii. a Mw.sub.A of less
than 130,000; and iii. An H.sub.A in the range of greater than or
equal to 0 to less than or equal to 30 J/g; and (b) a second
ethylene copolymer having: i. an E.sub.B in the range from greater
than or equal to 35 to less than or equal to 85; ii. a Mw.sub.B of
less than 70,000; and iii. An H.sub.B in the range of greater than
30 J/g to less than or equal to 60 J/g, wherein MI.sub.A/MI.sub.B
is less than or equal to 3.0 for the polymeric composition.
2. The polymeric composition of claim 1, wherein the first ethylene
copolymer and/or the second ethylene copolymer have a substantially
linear structure.
3. The polymeric composition of claim 1, wherein the first ethylene
copolymer and/or the second ethylene copolymer have a MWD of about
2.4 or less.
4. The polymeric composition of claim 1, wherein the MWD of the
first ethylene copolymer is in the range from greater than or equal
to 1.80 to less than or equal to 1.95, and/or wherein the MWD of
the second ethylene copolymer is in the range from greater than or
equal to 1.80 to less than or equal to 1.95.
5. The polymeric composition of claim 1, wherein E.sub.A is less
than E.sub.B for the polymeric composition, and/or wherein the
difference between E.sub.B and E.sub.A is greater than or equal to
5.
6. The polymeric composition of claim 1, wherein MI.sub.A/MI.sub.B
is less than or equal to 2.5 for the polymeric composition.
7. The polymeric composition of claim 1, wherein the weight percent
of the first ethylene copolymer in the polymeric composition is
greater than the weight percent of the second ethylene copolymer in
the polymeric composition.
8. The polymeric composition of claim 1, wherein the Mw.sub.A is
less than 90,000 and/or the Mw.sub.B is less than 60,000.
9. The polymeric composition of claim 1, wherein the first and/or
second ethylene copolymers comprises ethylene and a comonomer
selected from the group consisting of propylene, butene, hexene,
octene, and mixtures thereof
10. The polymeric composition of claim 1, wherein the comonomer of
the first and/or the second ethylene copolymers further comprises a
polyene monomer, and the polymeric composition further comprises up
to 5 mole % polyene-derived units.
11. A lubrication oil composition comprising: (a) a lubrication oil
basestock; and (b) the polymeric composition of claim 1.
12. The lubrication oil composition of claim 11 having at least one
of: (a) a TE of greater than or equal to 1.5; (b) a SSI of less
than 55; and (c) a complex viscosity at -31.degree. C. of less than
or equal to 500 cSt.
13. A process for making a polymeric composition comprising the
steps of: (a) copolymerizing ethylene and a first comonomer
component in the presence of a first metallocene catalyst in a
first polymerization reaction zone under first polymerization
conditions to produce a first effluent comprising the first
ethylene copolymer of claim 1; (b) copolymerizing ethylene and a
second comonomer component in the presence of a second metallocene
catalyst in a second polymerization reaction zone under second
polymerization conditions to produce a second effluent comprising
the second ethylene copolymer of claim 1; and (c) forming the
polymeric composition of claim 1, wherein the first and second
polymerization conditions are independently selected from the group
consisting of slurry phase, solution phase and bulk phase; and
wherein the first and second polymerization reaction zones are in
series, in parallel or the same.
14. The polymeric composition of claim 1, wherein H.sub.A is less
than H.sub.B for the polymeric composition.
15. The polymeric composition of claim 1, wherein H.sub.A is in the
range from greater than or equal to 0 to less than or equal to
10.
16. A rheology modifier for lubricators, comprising: a physical
blend comprising: (a) a first ethylene copolymer having: (i) an
E.sub.A of 35 to 60; (ii) a Mw.sub.A of 70,000 to 95,000; and (iii)
an H.sub.A of 0 J/g to 15 J/g; and (b) a second ethylene copolymer
having: (i) an E.sub.B of 45 to 75; (ii) a Mw.sub.B of 75,000 or
less; and (iii) an H.sub.B of 30 J/g to 60 J/g, wherein E.sub.B is
greater than E.sub.A and the physical blend has a MI.sub.A/MI.sub.B
of 3.0 or less.
17. The rheology modifier of claim 16, wherein the difference
between E.sub.B and E.sub.A is 10 or more.
18. The rheology modifier of claim 16, wherein Mw.sub.B is 65,000
to 75,000.
19. The rheology modifier of claim 16, wherein the first ethylene
copolymer and/or the second ethylene copolymer have a substantially
linear structure, and wherein the MWD of the first ethylene
copolymer is less than 3.0, and the MWD of the second ethylene
copolymer is 1.80 to 1.95.
20. The rheology modifier of claim 16, wherein the difference
between E.sub.B and E.sub.A is greater than or equal to 5, and
wherein MI.sub.A/MI.sub.B is less than or equal to 2.5 for the
polymeric composition.
21. The rheology modifier of claim 16, wherein the first and/or
second ethylene copolymers comprises ethylene and a comonomer
selected from the group consisting of propylene, butene, hexene,
octene, and mixtures thereof.
22. The rheology modifier of claim 16, wherein the comonomer of the
first and/or the second ethylene copolymers further comprises a
polyene monomer, and the polymeric composition further comprises up
to 5 mole % polyene-derived units.
23. A lubrication oil composition comprising: (a) a lubrication oil
basestock; and (b) the rheology modifier of claim 16.
24. The lubrication oil composition of claim 23, wherein the
composition comprises at least one of: (a) a TE of greater than or
equal to 1.5; (b) a SSI of less than 55; and (c) a complex
viscosity at -31.degree. C. of less than or equal to 500 cSt.
25. A process for making a rheology modifier of claim 16,
comprising: (a) copolymerizing ethylene and a first comonomer
component in the presence of a first metallocene catalyst in a
first polymerization reaction zone under first polymerization
conditions to produce a first effluent comprising the first
ethylene copolymer of claim 16; (b) copolymerizing ethylene and a
second comonomer component in the presence of a second metallocene
catalyst in a second polymerization reaction zone under second
polymerization conditions to produce a second effluent comprising
the second ethylene copolymer of claim 16; and (c) physically
blending the first and second ethylene copolymers to form the
rheology modifier of claim 16, wherein the first and second
polymerization conditions are independently selected from the group
consisting of slurry phase, solution phase and bulk phase.
Description
FIELD OF THE INVENTION
The present invention relates to polymeric compositions useful as
rheology modifiers and methods for making such compositions. More
particularly, the invention relates to compositionally disperse
polymeric compositions and/or crystallinity disperse polymeric
compositions that are useful in modifying the rheological
properties of fluids, and methods for making such compositions.
BACKGROUND OF THE INVENTION
Lubrication fluids are applied between moving surfaces to reduce
the friction between such surfaces, thereby improving efficiency
and reducing wear. Lubrication fluids also often function to
dissipate the heat generated by the moving surfaces.
One type of lubrication fluid is a petroleum-based lubrication oil
used for internal combustion engines. Lubrication oils contain
additives which help the lubrication oil to have a certain
viscosity at a given temperature. In general, the viscosity of
lubrication oils and fluids are inversely dependent upon
temperature. When the temperature of lubrication fluids is
increased, the viscosity of such fluids generally decreases, and
when the temperature is decreased, the viscosity of such fluids
generally increases. For internal combustion engines, for example,
it is desirable to have lower viscosity at low temperatures to
facilitate engine starting during cold weather, and a higher
viscosity at higher ambient temperatures when lubrication
properties typically decline.
Such additives for lubrication fluids and oils include rheology
modifiers, including viscosity index (VI) improvers. VI improving
components, derived from ethylene-alpha-olefin copolymers, modify
the rheological behavior to increase the lubricant viscosity, and
promote a more constant viscosity over the range of temperatures
over which the lubricant is used. Higher ethylene content
copolymers efficiently promote oil thickening and shear stability.
However, higher ethylene content copolymers tend to flocculate or
aggregate from oil formulations. This typically happens at ambient
or subambient conditions of controlled and quiescent cooling. This
deleterious property of otherwise advantageous higher ethylene
content viscosity improvers is measured by low temperature solution
rheology. Various remedies have been proposed for these higher
ethylene content copolymer formulations to overcome or mitigate
this propensity towards the formation of high viscosity flocculated
materials.
Conventional vanadium-based Ziegler-Natta catalysts are typically
most useful in polymerizing copolymers composed of ethylene and
propylene only. While copolymers of ethylene and higher
alpha-olefins, such as butene, may be produced, such copolymers are
limited to those having higher ethylene content.
Metallocene-based catalysts may be used to produce higher-alpha
olefin content in VI improvers, as noted in U.S. Pat. Nos.
6,525,007 and 5,446,221, which are incorporated herein by
reference.
The performance of VI improvers can be substantially improved, as
measured by the thickening efficiency (TE) and the shear stability
index (SSI), by appropriate and careful manipulation of the
structure of the VI improver. We have discovered that such
performance improves when the distribution of the monomers and the
chain architecture are controlled and segregated into at least two
compositionally disperse and/or crystallinity disperse polymeric
populations. These disperse polymeric populations may be achieved
by the use of a special synthesis process that employ
metallocene-based catalysts in the polymerization process.
Metallocene-based catalysts used in continuous feed stirred tank
reactor lead to ethylene copolymers which are compositionally
narrow and have a most probable narrow distribution in molecular
weight. Such a concomitant distribution of molecular weight and
composition would be characterized as a discrete component of the
VI improver.
One solution proposed is the use of blends of amorphous and
semi-crystalline ethylene copolymers for lubricant oil
formulations. The combination of two such ethylene-propylene
copolymers allows for increased TE, SSI, low temperature viscosity
performance and pour point. See, e.g., U.S. Pat. Nos. 7,402,235 and
5,391,617, and European Patent No. 0 638,611, the disclosures of
which are incorporated herein by reference.
We have found that, contrary to the teachings in the art, there is
a preferred relationship between the amount, composition and
molecular weight of the discrete distributions of the
ethylene-based alpha-olefin copolymers used in the polymeric blends
for VI improvers. This relationship leads to ethylene-based
alpha-olefin copolymers which have a controlled population of
monomers such that it has a superior performance in the TE at a
predetermined SSI. The choice of the alpha-olefin (e.g., propylene
or butene) will affect other properties of the rheology modifier
such as solubility parameter, TE and SSI. It is believed that the
addition of alpha-olefins may in addition lead to a further degree
of control in the polymer chain such that the level of
crystallinity will be diminished and thus the fluidity of the
solutions containing the polymers will be enhanced.
There remains a need, however, for novel rheology modifier
compositions comprised of ethylene and alpha-olefin-based
comonomers suitable for use in VI improvers which have unexpectedly
high TE as compared to the prior compositions while still being
equivalent in their beneficial low temperature solution rheology
properties. This invention meets this and other needs.
SUMMARY OF THE INVENTION
In one aspect, the invention relates to a polymeric composition
comprising: (a) a first ethylene copolymer having: i. an E.sub.A in
the range from greater than or equal to 35 to less than or equal to
60; and ii. a Mw.sub.A of less than or equal to 130,000; (b) a
second ethylene copolymer having: i. an E.sub.B in the range from
greater than or equal to 35 to less than or equal to 85; and ii. a
Mw.sub.B of less than 70,000.
In another aspect, the invention relates to a polymeric composition
comprising: (a) a first ethylene copolymer having: i. an H.sub.A in
the range from greater than or equal to 0 to less than or equal to
30; and ii. a Mw.sub.A of less than 130,000; (b) a second ethylene
copolymer having: i. an H.sub.B in the range from greater than 30
to less than or equal to 60; and ii. a Mw.sub.B of less than or
equal to 70,000.
In some embodiments, the polymeric composition has one or more of
the following properties: i. an E.sub.A less than E.sub.B; ii. an
H.sub.A less than H.sub.B; iii. a MI.sub.A/MI.sub.B less than or
equal to 3.0; and iv. the weight percent of the first ethylene
copolymer is greater than the weight percent of the second ethylene
copolymer in the polymeric composition.
In some embodiments of the polymeric composition, the first and the
second ethylene copolymers each comprise ethylene and one or more
comonomers. The comonomers may be independently selected from the
group consisting of alpha-olefins and mixtures thereof. The
alpha-olefins may be independently selected from the group
consisting of a C.sub.3 to C.sub.20 alpha-olefins and mixtures
thereof.
In another aspect, the invention relates to a lubrication oil
composition comprising: (a) a lubrication oil basestock; and (b)
any one of the polymeric compositions of this invention.
In another aspect, the invention relates to a process for making a
polymeric composition comprising the steps of: (a) copolymerizing
ethylene and a first comonomer component in the presence of a first
metallocene catalyst in a first polymerization reaction zone under
first polymerization conditions to produce a first effluent
comprising a first ethylene copolymer of the invention; (b)
copolymerizing ethylene and a second comonomer component in the
presence of a second metallocene catalyst in a second
polymerization reaction zone under second polymerization conditions
to produce a second effluent comprising a second ethylene copolymer
of the invention; and (c) forming a polymeric composition of the
invention, wherein the first and second polymerization conditions
are independently selected from the group consisting of slurry
phase, solution phase and bulk phase; and wherein the first and
second polymerization reaction zones are in series, in parallel or
the same.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 displays complex viscosity as a function of temperature for
the inventive and comparative polymeric compositions in PAO-4
lubrication basestock at a concentration of 2.5 wt. % from an
Anton-Parr rheometer.
FIG. 2 displays shear stress as a function of strain for the
inventive and comparative polymeric compositions in PAO-4
lubrication basestock at -15.degree. C. at a concentration of 2.5
wt. %.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to polymeric compositions useful as
rheology modifiers comprising polymeric compositions, including,
but not limited to, compositionally disperse polymeric compositions
and/or crystallinity disperse polymeric compositions that are
useful in modifying the rheological properties of lubrication
fluids. The compositionally disperse polymeric composition are
formed from at least two discrete compositions of ethylene
copolymers. The crystallinity disperse polymeric composition are
formed from ethylene copolymers having at least two discrete values
of residual crystallinity. The invention also relates to methods of
making such compositions.
The performance of ethylene-based rheology modifiers as VI
improvers is measured by the ratio of the TE to the SSI. It is
generally believed that the composition of the olefin copolymer at
a given SSI largely determines the TE, and that higher ethylene
content is preferred because of its TE. While increasing ethylene
content of rheology modifiers leads to improved TE/SSI ratios, it
also leads to increasing crystallinity of the olefin copolymer.
Increasing crystallinity, however, detracts from the performance or
the rheology modifier as a VI improver because crystalline polymers
tend to flocculate, either by themselves or in association with
other components of the lubrication oil and precipitate out of the
lubrication oils. These precipitates are apparent as regions (e.g.,
"lumps") of high viscosity or essentially complete solidification
(e.g., "gels") and can lead to clogs and blockages of pumps and
other passageways for the lubrication fluid and can lead to harm
and in some causes failure of moving machinery.
While not being bound by any particular theory, it is believed that
these rheology modifiers for lubrication fluids comprising
polymeric compositions which are compositionally disperse and/or
crystallinity disperse will be less prone to the deleterious
effects of macroscopic crystallization in dilute solution as
measured by the change in the rheology of the fluid solution
compared to an equivalent amount of a single ethylene copolymers of
the same average composition as the compositionally disperse blend.
It is also believed that these compositionally and/or crystallinity
disperse polymers will have lower crystallization on cooling from
ambient to sub-ambient temperatures, resulting in better low
temperature flow properties in solution as compared to equivalent
compositionally uniform polymers of similar molecular weight and
TE. These polymeric compositions and their use in lubrication oil
compositions with basestocks can be distinguished from other
compositionally monodisperse olefin copolymers by physical
separation of the compositionally disperse polymer into components
as well as by a higher ratio of the melting point by DSC to the
heat of fusion than would be observed for a monodisperse polymer of
the same average ethylene content, melt viscosity and
composition.
Dilute solutions of these inventive rheology modifiers display a
higher TE and lower shear stability than their comparatives at the
similar average composition which do not follow the invention
process. The rheology modifiers have a far superior low temperature
performance as measured by reduced viscosity of the solutions at
low temperature.
It is within the scope of the invention to have an unequal amount
of the internal olefin in each of the ethylene copolymer components
such that there is a preponderance of the internal olefin in the
higher ethylene copolymer component. In the limit, the invention
would lead to negligible amounts of internal olefin in the low
ethylene copolymer component, and mostly all of the internal olefin
in the higher ethylene copolymer component.
Definitions
For purposes of this inventions and the claims thereto, the
definitions set forth below are used.
As used herein, the term "complex viscosity" means a
frequency-dependent viscosity function determined during forced
small amplitude harmonic oscillation of shear stress, in units of
Pascal-seconds, that is equal to the difference between the dynamic
viscosity and the out-of-phase viscosity (imaginary part of complex
viscosity).
As used herein, the term "Composition Distribution Breadth Index"
(CDBI) is defined in U.S. Pat. No. 5,382,630, which is hereby
incorporated by reference. CDBI is defined as the weight percent of
the copolymer molecules having a comonomer content within 50% of
the median total molar comonomer content. The CDBI of a copolymer
is readily determined utilizing well known techniques for isolating
individual fractions of a sample of the copolymer. One such
technique is Temperature Rising Elution Fraction (TREF), as
described in L. Wild, et al., entitled "Determination of Branching
Distributions in Polyethylene and Ethylene Copolymers," Journal of
Polymer Science: Polymer Physics Edition, Vol. 20, pp. 441 (1982)
and U.S. Pat. No. 5,008,204, which are incorporated herein by
reference.
As used herein, the term "crystallinity disperse" means a polymeric
composition comprised of at least two ethylene-based copolymers
having two discrete values of residual crystallinity.
As used herein, the term "copolymer" includes any polymer having
two or more monomers.
As used herein, the term "crystallinity disperse" means a polymeric
composition comprised of at least two ethylene-based copolymers
having two discrete values of residual crystallinity.
As used herein, the term "disperse" means that the compositions
include constituent polymer fractions which have different
compositions and/or different crystallinity due, in part, to
different molecular weight distributions, and/or different monomer
compositional or sequence distributions.
As used herein, the term "E.sub.A" means the weight percent of
ethylene-derived units of the first ethylene copolymer based on the
weight of the polymeric composition.
As used herein, the term "E.sub.B" means the weight percent of
ethylene-derived units of the second ethylene copolymer based on
the weight of the polymeric composition.
As used herein, the term "ethylene copolymer" means an
ethylene-based copolymer comprised of ethylene and one or more
comonomers.
As used herein, the term "H.sub.A" means the heat of fusion in
units of joules/gram on a first melt of the first ethylene
copolymer.
As used herein, the term "H.sub.B" means the heat of fusion in
units of joules/gram on the first melt of the second ethylene
copolymer.
As used herein, the term "intermolecular composition distribution"
(InterCD or intermolecular CD), i.e., a measure of compositional
heterogeneity, defines the compositional heterogeneity in terms of
ethylene content, among polymer chains. It is expressed as the
minimum deviation, analogous to a standard deviation, in terms of
weight percent ethylene from the average ethylene composition for a
given copolymer sample needed to include a given weight percent of
the total copolymer sample which is obtained by excluding equal
weight fractions from both ends of the distribution. The deviation
need not be symmetrical. When expressed as a single number, for
example, an intermolecular composition distribution of 15 wt. %
shall mean the larger of the positive or negative deviations. For
example, at 50 wt. % intermolecular composition distribution the
measurement is akin to conventional composition distribution
breadth index.
As used herein, the term "intramolecular composition distribution"
(IntraCD or intramolecular CD) defines the compositional variation,
in terms of ethylene, within a copolymer chain. It is expressed as
the ratio of the alpha-olefin to ethylene along the segments of the
same chain.
As used herein, the term "MI.sub.A" means the melt index in units
of g/10 min or dg/min of the first ethylene copolymer.
As used herein, the term "MI.sub.B" means the melt index in units
of g/10 min or dg/min of the second ethylene copolymer.
As used herein, the term "Mn.sub.A" means the number-average
molecular weight of the first ethylene copolymer as measured by
GPC.
As used herein, the term "Mn.sub.B" means the number-average
molecular weight of the second ethylene copolymer as measured by
GPC.
As used herein, the term "Mw.sub.A" means the weight-average
molecular weight of the first ethylene copolymer in units of
grams/mole in terms of polystyrene, as measured by GPC.
As used herein, the term "Mw.sub.B" means the weight-average
molecular weight of the second ethylene copolymer in units of
grams/mole in terms of polystyrene, as measured by GPC.
As used herein, the term "MWD" means the ratio of Mw to Mn.
As used herein, the term "melting point" means the highest peak
among principal and secondary melting peaks as determined by DSC
during the second melt, as discussed herein.
As used herein, the term "mostly all" of the internal olefin is
intended to mean greater than 90 wt. % of the total amount of the
internal olefin contained in the higher ethylene copolymer
component, and greater than 5 wt. % of the total amount of the
internal olefin contained in the higher ethylene copolymer
component.
As used herein, the term "negligible amount" is intended to mean
less than 10 wt. % of the total amount of the internal olefin
contained in the polymeric composition, and less than 2 wt. % of
the total amount of internal olefin contained in the low ethylene
copolymer component.
As used herein, the term "polyene" means monomers or polymers
having two or more unsaturations, i.e., dienes, trienes, and the
like.
As used herein, the term "polypropylene" means a polymer made of at
least 50% propylene units, preferably at least 70% propylene units,
more preferably at least 80% propylene units, even more preferably
at least 90% propylene units, even more preferably at least 95%
propylene units, or 100% propylene units.
As used herein, the term "substantially linear structure" means
that the first ethylene copolymer and/or the second ethylene
copolymer is characterized as having less than 1 branch point
pendant with a carbon chain larger than 19 carbon atoms per 200
carbon atoms along a backbone.
When a polymer or copolymer is referred to as comprising an olefin,
including, but not limited to ethylene, propylene, and butene, the
olefin present in such polymer or copolymer is the polymerized form
of the olefin.
Polymeric Compositions
In one aspect of the invention, the rheology modifiers for
lubrication fluids comprise compositionally disperse polymeric
compositions and crystallinity disperse polymeric compositions.
These polymeric compositions comprise a first ethylene copolymer
blended with a second ethylene copolymer. Unless otherwise
specified, all references to first ethylene copolymer and second
ethylene copolymer refer to both the compositionally disperse
polymeric compositions and crystallinity disperse polymeric
compositions.
The first ethylene copolymer having relatively lower ethylene
content is a copolymer of ethylene, an alpha-olefin comonomer, and
optionally an internal olefin and optionally a polyene, such as a
diene.
The second ethylene copolymer having relatively higher
ethylene-content copolymer is a copolymer of ethylene, an internal
olefin, an alpha-olefin and optionally a polyene such as a
diene.
The referenced polymeric composition comprises a first ethylene
copolymer, preferably at least 51 wt. % of a first ethylene
copolymer based on the weight of the polymeric composition, and a
second ethylene copolymer, preferably 49 wt. % or less of a second
ethylene copolymer based on the weight of the polymeric
composition. In some embodiments, the first ethylene copolymer
comprises 60 wt. % of the first ethylene copolymer and 40 wt. % of
the second ethylene copolymer of the polymeric composition; in
other embodiments, the first ethylene copolymer comprises 70 wt. %
of the first ethylene copolymer and 30 wt. % of the second ethylene
copolymer of the polymeric composition; in still other embodiments,
the first ethylene copolymer comprises 80 wt. % of the first
ethylene copolymer and 20 wt. % of the second ethylene copolymer of
the polymeric composition; in still yet other embodiments, the
first ethylene copolymer comprises 90 wt. % of the first ethylene
copolymer and 10 wt. % of the second ethylene copolymer of the
polymeric composition.
In some embodiments of the compositionally disperse and/or
crystallinity disperse polymeric composition, the weight percent of
the first ethylene copolymer in the polymeric composition is
greater than the weight percent of the second ethylene copolymer in
the polymeric composition.
For compositionally disperse polymeric compositions, the first
ethylene copolymer is characterized by ethylene weight percent
(E.sub.A).
For crystallinity disperse polymeric compositions, the first
ethylene copolymer is characterized by a heat of fusion
(H.sub.A).
The first ethylene copolymer may be further characterized by a melt
index (MI.sub.A), a number-average molecular weight (Mn.sub.A), and
a weight-average molecular weight (Mw.sub.A).
The E.sub.A of the first ethylene copolymer is in the range of
35.ltoreq.E.sub.A.ltoreq.65; in some embodiments, in the range of
40.ltoreq.E.sub.A.ltoreq.60; in other embodiments, in the range of
45.ltoreq.E.sub.A.ltoreq.55; and in still yet other embodiments
E.sub.A is about 50.
The H.sub.A of the first ethylene copolymer is in the range of
0.ltoreq.H.sub.A.ltoreq.30; in some embodiments, in the range of
0.ltoreq.H.sub.A.ltoreq.15; in other embodiments, in the range of
0.ltoreq.H.sub.A.ltoreq.10; in still other embodiments, in the
range of 0.ltoreq.H.sub.A.ltoreq.5; and in still yet other
embodiments, H.sub.A is about 2.
The first ethylene copolymer may be characterized by a
weight-average molecular weight (Mw.sub.A) of less than or equal to
130,000, or less than 120,000, or less than 110,000, or less than
100,000, or less than 90,000, or less than 80,000, or less than
70,000. Preferably, the Mw.sub.A is from 70,000 to 95,000.
The first and/or second ethylene copolymers may be characterized by
a molecular weight distribution (MWD). The first and/or second
ethylene copolymer has a MWD of less than 3.0, or less than 2.4, or
less than 2.2, or less than 2.0. Preferably, the MWD for the first
ethylene copolymer and/or the second ethylene copolymer is in the
range of greater than or equal to 1.80 to less than or equal to
1.95.
For compositionally disperse polymeric compositions, the second
ethylene copolymer is characterized by ethylene weight percent
(E.sub.B).
For crystallinity disperse polymeric compositions, the second
ethylene copolymer is characterized by a heat of fusion
(H.sub.B).
The E.sub.B of the second ethylene copolymer is in the range of
35.ltoreq.E.sub.B.ltoreq.85; in some embodiments, in the range of
40.ltoreq.E.sub.B.ltoreq.80; in other embodiments, in the range of
45.ltoreq.E.sub.B.ltoreq.75; in still other embodiments, in the
range of 50.ltoreq.E.sub.B.ltoreq.70; and still yet other
embodiments, 55.ltoreq.E.sub.B.ltoreq.65; and still yet other
embodiments, E.sub.B is about 60.
The H.sub.B of the second ethylene copolymer is in the range of
30<H.sub.B.ltoreq.60; in some embodiments, in the range of
35<H.sub.B.ltoreq.55; in other embodiments, in the range of
40<H.sub.B.ltoreq.50; and still yet other embodiments, H.sub.B
is 45.
The second ethylene copolymer may be characterized by a
weight-average molecular weight (Mw.sub.B) of less than or equal to
75,000, or less than 70,000, or less than 65,000. Preferably, the
Mw.sub.A is from 65,000 to 75,000.
In some embodiments of the compositionally disperse polymeric
composition, the ethylene weight percent E.sub.A of the first
ethylene copolymer may be less than the ethylene weight percent
E.sub.B of the second ethylene copolymer for the polymeric
composition.
In some embodiments, the compositionally disperse polymeric
compositions may be characterized by the difference in the ethylene
weight percent, E.sub.B and E.sub.A. In some embodiments,
E.sub.B-E.sub.A.gtoreq.5; in other embodiments,
E.sub.B-E.sub.A.gtoreq.10; in still other embodiments,
E.sub.B-E.sub.A.gtoreq.15; in still yet other embodiments,
E.sub.B-E.sub.A.gtoreq.20. In some embodiments, the difference in
ethylene weight percent, E.sub.B and E.sub.A, is in the range of
8.ltoreq.E.sub.B-E.sub.A.ltoreq.10; in other embodiments, the
difference in E.sub.B and E.sub.A is 9.
In some embodiments of the crystallinity disperse polymeric
compositions, the heat of fusion H.sub.A of the first ethylene
copolymer may be less than the heat of fusion H.sub.B of the second
ethylene copolymer.
In some embodiments, the crystallinity disperse polymeric
compositions may be characterized by the difference in the heat of
fusion, H.sub.B and H.sub.A. In some embodiments,
H.sub.B-H.sub.A.gtoreq.4; in other embodiments,
H.sub.B-H.sub.A.gtoreq.8; in still other embodiments,
H.sub.B-H.sub.A.gtoreq.12; in still yet other embodiments,
H.sub.B-H.sub.A.gtoreq.16. In some embodiments, the difference in
the heat of fusion, H.sub.B and H.sub.A, is in the range of
8.ltoreq.H.sub.B-H.sub.A.ltoreq.10; in other embodiments, the
difference in H.sub.B and H.sub.A is 9.
The compositionally disperse and/or crystallinity disperse
polymeric composition may be further characterized by the ratio
MI.sub.A/MI.sub.B. In some embodiments, MI.sub.A/MI.sub.B is less
than or equal to 3, less than or equal to 2, less than or equal to
1.
The compositionally disperse and/or crystallinity disperse
polymeric compositions may be further characterized by the absolute
value of the difference in the melt index of the first ethylene
copolymer MI.sub.A and the melt index of the second ethylene
copolymer MI.sub.B. In some embodiments,
|MI.sub.A-MI.sub.B|.ltoreq.3.0; in other embodiments,
|MI.sub.A-MI.sub.B|.ltoreq.2.5; in still yet other embodiments,
|MI.sub.A-MI.sub.B|.ltoreq.2.0; in still yet other embodiments,
|MI.sub.A-MI.sub.B|.ltoreq.1.5; and still yet other embodiments,
|MI.sub.A-MI.sub.B|.ltoreq.1.1; and still yet other embodiments,
|MI.sub.A''MI.sub.B|.ltoreq.1.0.
The MFR of the compositionally disperse and/or crystallinity
disperse polymeric compositions will be intermediate to the MFR of
the lower and higher ethylene content copolymers when these
copolymers have different MFRs. The lower ethylene content
copolymer can have an MFR of from 0.2 to 25. The higher ethylene
content copolymer can have an MFR of from 0.2 to 25.
The first and/or second ethylene copolymers each comprise ethylene
and one or more comonomers. Preferably, the comonomer is
independently selected from the group consisting of alpha-olefins
and mixtures thereof. Preferably, the alpha-olefins are
independently selected from the group consisting of a C.sub.3 to
C.sub.20 alpha-olefins and mixtures thereof. Preferably, the
comonomer is propylene, butene, hexene, octene or mixtures
thereof.
In some embodiments, the comonomer of the first and the second
ethylene copolymers further comprises a polyene monomer. In such
embodiments, the compositionally disperse and crystallinity
disperse polymeric composition further comprises up to 5 mole %; up
to 4 mole %.; up to 3 mole %, up to 2 mole %, and up to 1 mole %
polyene-derived units.
In some embodiments, the first ethylene copolymer and/or the second
ethylene copolymer comprises one or more polymer fractions having a
different Mn.sub.A, a different Mw.sub.A, or a different
Mw.sub.A/Mn.sub.A distribution; Mn.sub.A is the number-average
molecular weight of the first ethylene copolymer, and Mw.sub.A is
the weight-average molecular weight of the first ethylene
copolymer.
In some embodiments, the rheology modifier has first ethylene
copolymer and/or the second copolymer polymer fractions having
different comonomer insertion sequences.
In some embodiments, the first or second ethylene copolymer of the
compositionally disperse polymeric composition has a substantially
linear structure.
The substantially linear structure of the first ethylene copolymer
and/or the second ethylene copolymer has less than 1 branch point
pendant with a carbon chain larger than 19 carbon atoms per 200
carbon atoms along a backbone, less than 1 branch point pendant
with a carbon chain larger than 19 carbon atoms per 300 branch
points, less than 1 branch point pendant with a carbon chain larger
than 19 carbon atoms per 500 carbon atoms and preferably less than
1 branch point pendant with a carbon chain larger than 19 carbon
atoms per 1000 carbon atoms notwithstanding the presence of branch
points due to incorporation of the comonomer.
Comonomer Components
In embodiments of this invention, suitable comonomers include, but
are not limited to, propylene (C.sub.3) and other alpha-olefins,
such as C.sub.4 to C.sub.20 alpha-olefins (also referred to herein
as ".alpha.-olefins"), and preferably propylene and C.sub.4 to
C.sub.12 .alpha.-olefins. The .alpha.-olefin comonomer can be
linear or branched, and two or more comonomers can be used, if
desired. Thus, reference herein to "an alpha-olefin comonomer"
includes one, two, or more alpha-olefin comonomers.
Examples of suitable comonomers include propylene, linear C.sub.4
to C.sub.12 .alpha.-olefins, and .alpha.-olefins having one or more
C.sub.1 to C.sub.3 alkyl branches. Specific examples include:
propylene; 1-butene; 3-methyl-1-butene; 3,3-dimethyl-1-butene;
1-pentene; 1-pentene with one or more methyl, ethyl, or propyl
substituents; 1-hexene with one or more methyl, ethyl, or propyl
substituents; 1-heptene with one or more methyl, ethyl, or propyl
substituents; 1-octene with one or more methyl, ethyl, or propyl
substituents; 1-nonene with one or more methyl, ethyl, or propyl
substituents; ethyl, methyl, or dimethyl-substituted 1-decene, or
1-dodecene. Preferred comonomers include: propylene; 1-butene;
1-pentene; 3-methyl-1-butene; 1-hexene; 3-methyl-1-pentene;
4-methyl-1-pentene; 3,3-dimethyl-1-butene; 1-heptene; 1-hexene with
a methyl substituents on any of C.sub.3 to C.sub.5; 1-pentene with
two methyl substituents in any stoichiometrically acceptable
combination on C.sub.3 or C.sub.4; 3-ethyl-1-pentene, 1-octene,
1-pentene with a methyl substituents on any of C.sub.3 or C.sub.4;
1-hexene with two methyl substituents in any stoichiometrically
acceptable combination on C.sub.3 to C.sub.5; 1-pentene with three
methyl substituents in any stoichiometrically acceptable
combination on C.sub.3 or C.sub.4; 1-hexene with an ethyl
substituents on C.sub.3 or C.sub.4; 1-pentene with an ethyl
substituents on C.sub.3 and a methyl substituents in a
stoichiometrically acceptable position on C.sub.3 or C.sub.4;
1-decene, 1-nonene, 1-nonene with a methyl substituents on any of
C.sub.3 to C.sub.9; 1-octene with two methyl substituents in any
stoichiometrically acceptable combination on C.sub.3 to C.sub.7;
1-heptene with three methyl substituents in any stoichiometrically
acceptable combination on C.sub.3 to C.sub.6; 1-octene with an
ethyl substituents on any of C.sub.3 to C.sub.7; 1-hexene with two
ethyl substituents in any stoichiometrically acceptable combination
on C.sub.3 or C.sub.4; and 1-dodecene.
Polyene Components
The polyenes particularly useful as co-monomers are non-conjugated
dienes, preferably they are straight chain, hydrocarbon di-olefins
or cycloalkenyl-substituted alkenes, having about 6 to about 15
carbon atoms, for example: (a) straight chain acyclic dienes, such
as 1,4-hexadiene and 1,6-octadiene; (b) branched chain acyclic
dienes, such as 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6; (c)
single ring alicyclic dienes, such as 1,4-cyclohexadiene;
1,5-cyclo-octadiene and 1,7-cyclododecadiene; (d) multi-ring
alicyclic fused and bridged ring dienes, such as: tetrahydroindene,
norbornadiene, methyl-tetrahydroindene, dicyclopentadiene (DCPD),
bicyclo-(2.2.1)-hepta-2,5-diene, alkenyl, alkylidene, cycloalkenyl
and cycloalkylidene norbornenes, such as 5-methylene-2-norbornene
(MNB), 5-propenyl-2-norbornene, 5-isopropylidene-2-norbornene,
5-(4-cyclopentenyl)-2-norbornene, 5-cyclohexylidene-2-norbornene,
and 5-vinyl-2-norbornene (VNB); and (e) cycloalkenyl-substituted
alkenes, such as vinyl cyclohexene, allyl cyclohexene, vinyl
cyclooctene, 4-vinyl cyclohexene, allyl cyclodecene; and vinyl
cyclododecene. Of the non-conjugated dienes typically used, the
preferred dienes are dicyclopentadiene (DCPD), 1,4-hexadiene,
1,6-octadiene; 5-methyl-1,4-hexadiene; 3,7-dimethyl-1,6-octadiene;
5-methylene-2-norbornene, 5-ethylidene-2-norbornene (ENB), and
tetracyclo (.DELTA.-11,12) 5,8 dodecene. It is preferred to use
dienes which do not lead to the formation of long chain branches.
For successful use as rheology modifiers, such as VI improver non-
or lowly branched polymer chains are preferred. Other polyenes that
can be used include cyclopentadiene and octatetra-ene; and the
like.
Polymerization Process
In another aspect, the present invention is directed to a
polymerization process for making rheology modifiers comprised of
compositionally disperse polymer compositions and/or crystallinity
disperse polymeric compositions.
In some embodiments of this invention, the process for making a
rheology modifier composition for lubrication fluids comprising a
compositionally disperse polymeric composition or a crystallinity
disperse polymeric composition comprises the steps of: (a)
copolymerizing ethylene and a first comonomer component in the
presence of a first metallocene catalyst in a first polymerization
reaction zone under first polymerization conditions to produce a
first effluent comprising any one of the first ethylene copolymers
of this invention; (b) copolymerizing ethylene and a second
comonomer component in the presence of a second metallocene
catalyst in a second polymerization reaction zone under second
polymerization conditions to produce a second effluent comprising
any one of the second ethylene copolymers of this invention; and
(c) forming any one of the polymeric compositions of this
invention.
In one or more embodiments, the first and second polymerization
conditions of the invention are independently selected from the
group consisting of slurry phase, solution phase and bulk phase.
When the first and second polymerization conditions are solution
phase, and the forming step (c) comprises the substantial removal
of the solvent from the second effluent to produce a solid
polymeric composition.
In one embodiment, separate polymerizations may be performed in
parallel with the effluent polymer solutions from two reactors
combined downstream before the finishing. In another embodiment,
separate polymerizations may be performed in series, where the
effluent of one reactor is fed to the next reactor. In still
another embodiment, the separate polymerization may be performed in
the same reactor, preferably in sequential polymerizations.
In a preferred embodiment, ethylene copolymers are polymerized by a
metallocene catalyst, to form the first ethylene copolymer in one
reactor and the second ethylene copolymer in another reactor. The
ethylene copolymers are combined and then subjected to finishing
steps to produce a solid polymeric composition. The first ethylene
copolymer can be made first; alternatively, the second ethylene
copolymer can be made first in a series reactor configuration or
both ethylene copolymers can be made simultaneously in a parallel
reactor configuration.
Each polymerization reaction is preferably carried out in a
continuous flow, stirred tank reactor. When polymerizing in a
series reactor layout, the polymeric product emerging from the
second reactor is an intimate blend of the first ethylene copolymer
and the second ethylene copolymer.
Particular reactor configurations and processes suitable for use in
the processes of the present invention are described in detail in
U.S. Pat. Nos. 6,319,998, and 6,881,800, the disclosures of which
are incorporated herein by reference. The later developments of the
general approach is to separately polymerize the two copolymers in
an alkane solvent, either hexane in a solution process or propylene
in a slurry process, and to finish the polymers to remove the
solvent.
The metallocene catalysts, and their use with non-coordinating ions
and non-ionic activators used in the polymerization process, are
taught in U.S. Provisional Patent App. No. 61/173,528, incorporated
herein by reference.
Examples of suitable bis-cyclopentadienyl metallocenes, include,
but are not limited to, the type disclosed in U.S. Pat. Nos.
5,324,800; 5,198,401; 5,278,119; 5,387,568; 5,120,867; 5,017,714;
4,871,705; 4,542,199; 4,752,597; 5,132,262; 5,391,629; 5,243,001;
5,278,264; 5,296,434; and 5,304,614, all of which are incorporated
by reference.
Lubrication Oil Composition
The lubrication oil composition according to the invention
comprises a lubrication oil basestock and any one of the
compositionally disperse polymeric composition of this invention
and/or any one of the crystallinity disperse polymeric composition
of this invention, an optionally, a pour point depressant. In some
embodiments, such lubrication oil compositions have the following
properties: (a) a thickening efficiency greater than 1.5, or
greater than 1.7, or greater than 1.9, or greater than 2.2, or
greater than 2.4 or greater than 2.6; (b) a shear stability index
less than 55, or less than 45, or less than 35, or less than 30, or
less than 25, or less than 20, or less than 15; and/or (c) a
complex viscosity at -35.degree. C. of less than 500, or less than
450, or less than 300, or less than 100, or less than 50, or less
20, or less than 10 centistokes (cSt).
The lubrication oil composition preferably comprises 2.5 wt. %, or
1.5 wt. %, or 1.0 wt. % or 0.5 wt. % of the compositionally
disperse and/or crystallinity disperse polymeric composition.
The components for forming the lubrication oil basestock are
described below.
Lubrication Oil Basestock
Examples of the lubrication oil bases for use in the invention
include, but are not limited to, mineral oils and synthetic oils
such as poly-.alpha.-olefins, polyol esters and polyalkylene
glycols. A mineral oil or a blend of a mineral oil and synthetic
oil is preferably employed. The mineral oil is generally used after
subjected to purification such as dewaxing.
Although mineral oils are divided into several classes according to
the purification method, generally used is a mineral oil having a
wax content of 0.5 to 10%. Further, a mineral oil having a
kinematic viscosity of 10 to 200 cSt is generally used.
Lubricant Formulations
In one embodiment, the polymeric composition is used as a VI
improver for an oil composition. The polymer composition has
solubility in oil of at least 10 wt. %. From 0.001 to 49 wt. % of
this composition is incorporated into basestock oil, such as
lubrication oil or a hydrocarbon fuel, depending upon whether the
desired product is a finished product or an additive concentrate.
The amount of the VI improver is an amount which is effective to
improve or modify the VI of the basestock oil, i.e., a viscosity
improving effective amount. Generally, this amount is from 0.001 to
20 wt. % for a finished product (e.g., a fully formulated
lubrication oil composition), with alternative lower limits of
0.01%, 0.1% or 1%, and alternative upper limits of 15% or 10%, in
other embodiments. Ranges of VI improver concentration from any of
the recited lower limits to any of the recited upper limits are
within the scope of the present invention, and one skilled in the
art can readily determine the appropriate concentration range based
upon the ultimate solution properties.
Basestock oils suitable for use in preparing the lubrication
compositions of the present invention include those conventionally
employed as crankcase lubrication oils for spark-ignited and
compression-ignited internal combustion engines, such as automobile
and truck engines, marine and railroad diesel engines, and the
like. Advantageous results are also achieved by employing the VI
improver compositions of the present invention in basestock oils
conventionally employed in and/or adapted for use as power
transmitting fluids such as automatic transmission fluids, tractor
fluids, universal tractor fluids and hydraulic fluids, heavy duty
hydraulic fluids, power steering fluids and the like. Gear
lubricants, industrial oils, pump oils and other lubrication oil
compositions can also benefit from the incorporation therein of the
additives of the present invention.
The lubrication oils to which the products of this invention can be
added include not only hydrocarbon oils derived from petroleum, but
also include synthetic lubrication oils such as esters of dibasic
acids; complex esters made by etherification of monobasic acids,
polyglycols, dibasic acids and alcohols; polyolefin oils, etc.
Thus, the VI improver compositions of the present invention may be
suitably incorporated into synthetic basestock oils such as alkyl
esters of dicarboxylic acids, polyglycols and alcohols;
polyalpha-olefins; polybutenes; alkyl benzenes; organic esters of
phosphoric acids; polysilicone oils; etc. The VI compositions of
the present invention can also be utilized in a concentrate form,
such as from 1 wt. % to 49 wt. % in oil, e.g., mineral lubrication
oil, for ease of handling, and may be prepared in this form by
carrying out the reaction of the invention in oil as previously
described.
The above oil compositions may optionally contain other
conventional additives, such as, for example, pour point
depressants, antiwear agents, antioxidants, other viscosity-index
improvers, dispersants, corrosion inhibitors, anti-foaming agents,
detergents, rust inhibitors, friction modifiers, and the like.
Compositions when containing these conventional additives are
typically blended into the basestock oil in amounts which are
effective to provide their normal attendant function. Thus, typical
formulations can include, in amounts by weight, a VI improver of
the present invention (0.01-12%); a corrosion inhibitor (0.01-5%);
an oxidation inhibitor (0.01-5%); depressant (0.01-5%); an
anti-foaming agent (0.001-3%); an anti-wear agent (0.001-5%); a
friction modifier (0.01-5%); a detergent/rust inhibitor (0.01-10%);
and an oil basestock.
When other additives are used, it may be desirable, although not
necessary, to prepare additive concentrates comprising concentrated
solutions or dispersions of the VI improver (in concentrate amounts
hereinabove described), together with one or more of the other
additives, such a concentrate denoted an "additive package,"
whereby several additives can be added simultaneously to the
basestock oil to form a lubrication oil composition. Dissolution of
the additive concentrate into the lubrication oil may be
facilitated by solvents and by mixing accompanied with mild
heating, but this is not essential. The additive-package will
typically be formulated to contain the VI improver and optional
additional additives in proper amounts to provide the desired
concentration in the final formulation when the additive-package is
combined with a predetermined amount of base lubricant. Thus, the
products of the present invention can be added to small amounts of
basestock oil or other compatible solvents along with other
desirable additives to form additive-packages containing active
ingredients in collective amounts of typically from 2.5 to 90 wt.
%, preferably from 5 to 75 wt. %, and still more preferably from 8
to 50 wt. % additives in the appropriate proportions with the
remainder being basestock oil.
The final formulations may use typically about 10 wt. % of the
additive-package with the remainder being basestock oil.
Blending with Basestock Oils
Conventional blending methods are described in U.S. Pat. No.
4,464,493, the disclosure of which is incorporated herein by
reference. This conventional process requires passing the polymer
through an extruder at elevated temperature for degradation of the
polymer and circulating hot oil across the die face of the extruder
while reducing the degraded polymer to particle size upon issuance
from the extruder and into the hot oil. The pelletized, solid
polymer compositions of the present invention, as described above,
can be added by blending directly with the basestock oil so as give
directly viscosity for the VI improver, so that the complex
multi-step process of the prior art is not needed. The solid
polymer composition can be dissolved in the basestock oil without
the need for additional shearing and degradation processes.
The polymer compositions will be soluble at room temperature in
lube oils at up to 10 percent concentration in order to prepare a
viscosity modifier concentrate. Such concentrate, including
eventually an additional additive package including the typical
additives used in lube oil application as described above, is
generally further diluted to the final concentration (usually
around 1%) by multi-grade lube oil producers. In this case, the
concentrate will be a pourable homogeneous solid free solution.
The polymer compositions preferably have a SSI (determined
according to ASTM D97) of from 10 to 50.
Specific Embodiments
Specific numbered embodiments of the invention can further include:
Embodiment 1: A polymeric composition comprising: (a) a first
ethylene copolymer having: (i) an intermolecular composition
distribution of greater than or equal to 50, 40, 30, 20, 10 or 5
wt. %; and (ii) a substantially linear structure; and (b) a second
ethylene copolymer having: (i) an intermolecular composition
distribution of less than or equal to 50, 40, 30, 20, 10 or 5 wt.
%; and (ii) a substantially linear structure. Embodiment 2: A
polymeric composition for lubrication fluids comprising: (a) a
first ethylene copolymer having: (i) an intermolecular composition
distribution of greater than or equal to 50, 40, 30, 20, 10 or 5
wt. %; (ii) a substantially linear structure; and (b) a second
ethylene copolymer having: (i) an intramolecular composition
distribution of less than or equal to 50, 40, 30, 20, 10 or 5 wt.
%; and (ii) a substantially linear structure. Embodiment 3: A
polymeric composition comprising: (a) a first ethylene copolymer
having: (i) an intramolecular composition distribution of greater
than or equal to 50, 40, 30, 20, 10 or 5 wt. %; (ii) a
substantially linear structure; and (b) a second ethylene copolymer
having: (i) an intermolecular composition distribution of less than
or equal to 50, 40, 30, 20, or 5 wt. %; and (ii) a substantially
linear structure. Embodiment 4: A polymeric composition comprising:
(a) a first ethylene copolymer having: (i) an intramolecular
composition distribution of greater than or equal to 50, 40, 30,
20, 10, or 5 wt. %, (ii) a substantially linear structure; and (b)
a second ethylene copolymer having: (i) an intramolecular
composition distribution of less than or equal to 50, 40, 30, 20,
or 5 wt. %, and (ii) a substantially linear structure. Embodiment
5: The polymeric composition of Embodiments 1 to 4, wherein the
ethylene content of the first ethylene copolymer (E.sub.A) or the
ethylene content of the second ethylene copolymer (E.sub.B) is in
the range from greater than or equal to 35 to less than or equal to
85 based on the weight of the polymeric composition. Embodiment 6:
The polymeric composition of Embodiments 1 to 4, wherein the
absolute value of the difference between E.sub.B and E.sub.A is
greater than or equal to 5 wt. %. Embodiment 7: The polymeric
composition of Embodiments 1 to 4, wherein the first ethylene
copolymer and/or the second ethylene copolymers each comprises
ethylene and a comonomer. The comonomer is independently selected
from the group consisting of alpha-olefins and mixtures thereof.
The alpha-olefins are independently selected from the group
consisting of a C.sub.3 to C.sub.20 alpha-olefins and mixtures
thereof. The alpha-olefins are propylene, butene, hexene, octene or
mixtures thereof. Embodiment 8: The polymeric composition of
Embodiments 1 to 4, wherein the comonomer of the first and/or the
second ethylene copolymers further comprises a polyene monomer, and
the polymeric composition further comprises up to 5 mole %
polyene-derived units. Embodiment 9: A lubrication oil composition
comprising: (a) a lubrication oil basestock; and (b) any one the
Embodiments 1 to 4 of the polymeric composition. The lubrication
oil composition having a physical property selected from the group
consisting of: (i) a TE of greater than or equal to 1.5; (ii) a SSI
of less than 55; and (iii) a complex viscosity at -31.degree. C. of
less than or equal to 500 cSt. Polymer Analyses
The ethylene content as an ethylene weight percent (C.sub.2 wt. %)
for the ethylene copolymers were determined according to ASTM
D1903.
DSC Measurements of the crystallization temperature, T.sub.c, and
melting temperature, T.sub.m, of the ethylene copolymers were
measured using a TA Instruments Model 2910 DSC. Typically, 6-10 mg
of a polymer was sealed in a pan with a hermetic lid and loaded
into the instrument. In a nitrogen environment, the sample was
first cooled to -100.degree. C. at 20.degree. C./min. It was heated
to 220.degree. C. at 10.degree. C./min and melting data (first
heat) were acquired. This provides information on the melting
behavior under as-received conditions, which can be influenced by
thermal history as well as sample preparation method. The sample
was then equilibrated at 220.degree. C. to erase its thermal
history. Crystallization data (first cool) were acquired by cooling
the sample from the melt to -100.degree. C. at 10.degree. C./min
and equilibrated at -100.degree. C. Finally it was heated again to
220.degree. C. at 10.degree. C./min to acquire additional melting
data (second heat). The endothermic melting transition (first and
second heat) and exothermic crystallization transition (first cool)
were analyzed for peak temperature and area under the peak. The
term "melting point," as used herein, is the highest peak among
principal and secondary melting peaks as determined by DSC during
the second melt, discussed above. The thermal output is recorded as
the area under the melting peak of the sample, which is typically
at a maximum peak at about 30.degree. C. to about 175.degree. C.
and occurs between the temperatures of about 0.degree. C. and about
200.degree. C. The thermal output is measured in Joules as a
measure of the heat of fusion. The melting point is recorded as the
temperature of the greatest heat absorption within the range of
melting of the sample.
Molecular weight (weight-average molecular weight, M.sub.w,
number-average molecular weight, M.sub.n, and molecular weight
distribution, M.sub.w/M.sub.n or MWD) were determined using a High
Temperature Size Exclusion Chromatograph (either from Waters
Corporation or Polymer Laboratories), equipped with a differential
refractive index detector (DRI), an online light scattering (LS)
detector, and a viscometer. Experimental details not described
below, including how the detectors were calibrated, are described
in: T. Sun et al., "Effect of Short Chain Branching on the Coil
Dimensions of Polyolefins in Dilute Solution," Macromolecules,
Volume 34, Issue 19, pp. 6812-6820, (2001).
Three Polymer Laboratories PLgel 10 mm Mixed-B columns were used.
The nominal flow rate was 0.5 cm.sup.3/min, and the nominal
injection volume was 300 .mu.L. The various transfer lines, columns
and differential refractometer (the DRI detector) were contained in
an oven maintained at 145.degree. C. Solvent for the SEC experiment
was prepared by dissolving 6 grams of butylated hydroxy toluene as
an antioxidant in 4 liters of Aldrich reagent grade 1, 2, 4
trichlorobenzene (TCB). The TCB mixture was then filtered through a
0.7 .mu.m glass pre-filter and subsequently through a 0.1 .mu.m
Teflon filter. The TCB was then degassed with an online degasser
before entering the SEC. Polymer solutions were prepared by placing
dry polymer in a glass container, adding the desired amount of TCB,
then heating the mixture at 160.degree. C. with continuous
agitation for about 2 hours. All quantities were measured
gravimetrically. The TCB densities used to express the polymer
concentration in mass/volume units are 1.463 g/ml at room
temperature and 1.324 g/ml at 145.degree. C. The injection
concentration ranged from 1.0 to 2.0 mg/ml, with lower
concentrations being used for higher molecular weight samples.
Prior to running each sample the DRI detector and the injector were
purged. Flow rate in the apparatus was then increased to 0.5
ml/minute, and the DRI was allowed to stabilize for 8-9 hours
before injecting the first sample. The LS laser was turned on 1 to
1.5 hours before running samples.
The concentration, c, at each point in the chromatogram is
calculated from the baseline-subtracted DRI signal, I.sub.DRI,
using the following equation: c=K.sub.DRII.sub.DRI/(dn/dc) where
K.sub.DRI is a constant determined by calibrating the DRI, and
(dn/dc) is the same as described below for the light scattering
(LS) analysis. Units on parameters throughout this description of
the SEC method are such that concentration is expressed in
g/cm.sup.3, molecular weight is expressed in g/mole, and intrinsic
viscosity is expressed in dL/g.
The light scattering detector used was a Wyatt Technology High
Temperature mini-DAWN. The polymer molecular weight, M, at each
point in the chromatogram is determined by analyzing the LS output
using the Zimm model for static light scattering (M. B. Huglin,
Light Scattering from Polymer Solutions, Academic Press, 1971):
.times..DELTA..times..times..function..theta..function..theta..times..tim-
es. ##EQU00001## Here, .DELTA.R(.theta.) is the measured excess
Rayleigh scattering intensity at scattering angle .theta., c is the
polymer concentration determined from the DR1 analysis, A.sub.2 is
the second virial coefficient [for purposes of this invention and
the claims thereto, A.sub.2=0.0006 for propylene polymers and 0.001
otherwise], P(.theta.) is the form factor for a monodisperse random
coil (M. B. Huglin, Light Scattering from Polymer Solutions,
Academic Press, 1971), and K.sub.o is the optical constant for the
system:
.times..pi..times..function..times..times..times..times..lamda..times.
##EQU00002## in which N.sub.A is Avogadro's number, and (dn/dc) is
the refractive index increment for the system. The refractive
index, n=1.500 for TCB at 145.degree. C. and .lamda.=690 nm. For
purposes of this invention and the claims thereto (dn/dc)=0.104 for
propylene polymers and 0.1 otherwise.
A high temperature Viscotek Corporation viscometer, which has four
capillaries arranged in a Wheatstone bridge configuration with two
pressure transducers, was used to determine specific viscosity. One
transducer measures the total pressure drop across the detector,
and the other, positioned between the two sides of the bridge,
measures a differential pressure. The specific viscosity,
.eta..sub.s, for the solution flowing through the viscometer is
calculated from their outputs. The intrinsic viscosity, [.eta.], at
each point in the chromatogram is calculated from the following
equation: .eta..sub.s=c[.eta.]+0.3(c[.eta.]).sup.2 where c is
concentration and was determined from the DRI output.
The branching index (g') is calculated using the output of the
SEC-DRI-LS-VIS method as follows. The average intrinsic viscosity,
[.eta.].sub.avg, of the sample is calculated by:
.eta..function..eta. ##EQU00003## where the summations are over the
chromatographic slices, i, between the integration limits. The
branching index g' is defined as:
'.eta..alpha. ##EQU00004## where, for purpose of this invention and
claims thereto, .alpha.=0.695 for ethylene, propylene, and butene
polymers; and k=0.000579 for ethylene polymers, k=0.000228 for
propylene polymers, and k=0.000181 for butene polymers. M.sub.v is
the viscosity-average molecular weight based on molecular weights
determined by LS analysis.
Anton-Parr Low Temperature Solution Rheology (low temperature
rheology) experiments were done on an Anton-Parr Model MCR501
rheometer using a 1'' cone and plate setup. The cone has a nominal
1 degree angle and 50 micron gap. About 100 microliters of sample
is deposited on the bottom plate using a syringe-pipette. The cone
is then lowered onto the plate so that the volume between the cone
and plate is fully occupied by solution. The temperature is then
lowered at a cooling rate of 1.5.degree. C./min. while measuring
the complex viscosity at an angular frequency of 0.1 radians/sec.
applying a 10% strain and recording a value every minute. The
viscosity at 0.1 rad/sec is then plotted as a function of
temperature to observe the effect of gelation.
Melt Index (MI) was measured according to ASTM D1238 at 190.degree.
C. under a 2.16 kilogram load.
Melt Flow Rate (MFR) was measured according to ASTM D1238 at
230.degree. C. under a 2.16 kilogram load or a 21.6 kilogram
load.
Thickening Efficiency (TE) was determined according to ASTM
D445.
Shear Stability index (SSI) was determined according to ASTM D6278
at 30 and 90 passes using a Kurt Ohban machine.
Shear stress data was accomplished by first heating the sample to
-15.degree. C., and waiting for 15 minutes. Then while measuring
the shear stress, applying a logarithmically increasing strain by
varying the shear rate logarithmically from 10.sup.-3 to 10 with 20
points/decade and 1 second per point.
The number of branch points was determined by measuring the radius
of gyration of polymers as a function of the molecular weight by
the methods of size exclusion chromatography augmented by laser
light scattering. These procedures are described in the
publications "A Study of the Separation Principle in Size Exclusion
Chromatography," by T. Sun et al., in the journal Macromolecules,
Volume 37, Issue 11, pp. 4304-4312, (2004), and "Effect of Short
Chain Branching on the Coil Dimensions of Polyolefins in Dilute
Solution" by T. Sun et al., in the journal Macromolecules, Volume
34, Issue 19, pp. 6812-6820, (2001), which are both incorporated by
reference.
Branching in polymers having narrow, and most probably, low
polydispersity index with essentially uniform intramolecular and
intermolecular distribution of composition can also be described by
the ratio of the TE to the MFR@230.degree. C. measured at a load of
2.16 Kg. High values of this parameter indicate low levels of
branching while low levels indicate substantial levels of
branching.
Intermolecular composition distribution, unlike CDBI, contemplates
weight percent of copolymer content within a smaller range from a
median total molar comonomer content, e.g., within 25 wt. % of
median. For example, for a Gaussian compositional distribution,
95.5% of the polymer, used herein for this example as "Polymer
Fraction", is within 20 wt. % ethylene of the mean if the standard
deviation is 10%. The intermolecular composition distribution for
the Polymer Fraction is 20 wt. % ethylene for such a sample, i.e.,
10% standard deviation yields 20 wt. % intermolecular composition
distribution.
Compositional Heterogeneity, both intermolecular-CD and
intramolecular-CD can be determined by carbon-13 NMR. Conventional
techniques for measuring intermolecular-CD and intramolecular-CD
are described in Macromolecules, H. N. Cheng et al., entitled
".sup.13C NMR Analysis of Compositional Heterogeneity in
Ethylene-Propylene Copolymers," Volume 24, Issue 8, pp. 1724-1726,
(1991), and in the publication Macromolecules, C. Cozewith,
entitled "Interpretation of .sup.13C NMR Sequence Distribution for
Ethylene-Propylene Copolymers Made with Heterogeneous Catalysts",
Volume 20, Issue 6, pp. 1237-1244, (1987).
Generally, conventional carbon-13 NMR measurements of diad and
triad distribution is used to characterize the ethylene-based
copolymer. Any conventional technique for measuring carbon-13 NMR
may be utilized. For example, ethylene-based copolymer samples are
dissolved in a solvent, e.g., trichlorobenzene at 4.5 wt. %
concentration. The carbon-13 NMR spectra are obtained at elevated
temperature, e.g., 140.degree. C., on a NMR spectrometer at 100
MHz. An exemplary spectrometer is a pulsed Fourier transform Varian
XL-400 NMR spectrometer. Deuteriated o-dichlorobenezene is placed
in a coaxial tube to maintain an internal lock signal. The
following instrument conditions are utilized: pulse angle,
75.degree.; pulse delay, 25 second; acquisition time, 0.5 second;
sweep width, 16000 Hz. The carbon-13 NMR peak area measurements
were determined by spectral integration. Diad and triad
concentrations were calculated from the equations presented in
Macromolecules, Kakugo et al., entitled ".sup.13C NMR Determination
of Monomer Sequence Distribution in Ethylene-Propylene Copolymers
Prepared with .delta.-TiCl.sub.3--Al(C.sub.2H.sub.5).sub.2Cl,"
Volume 15, Issue 4, pp. 1150-1152, (1982). The diad and triad
concentrations were then normalized to give a mole fraction
distribution. Polymer composition was calculated from the methane
peaks, the methylene peaks, and the diad balance. These values may
be considered individually or an average of the three values may be
utilized. Unless stated otherwise, this application utilizes an
average of these three values. The results are then compared to
conventional model equations as disclosed in the above
references.
One aspect of these measurements involves the determination of the
reactivity ratios (r.sub.1r.sub.2) of the polymerization system for
the ethylene-based polymers according to the procedures in the
publication. Polymers which have a compositional heterogeneity,
either intramolecular or intermolecular, have a much larger
reactivity ratio than the polymers which have only a small or
negligible amount.
Without being limited to theory or one method of calculation, it is
believed that an one exemplary model for, so called ideal
copolymerizations, is described by the terminal copolymerization
model: m=M(r.sub.1M+1)/(r.sub.2+M) (1) Wherein r.sub.1 and r.sub.2
are the reactivity ratios, m is the ratio of monomers in the
copolymer, m.sub.i/m.sub.2, M is the ratio of monomers in the
reactor, M.sub.1/M.sub.2, and the diad and triad concentrations
follow first order Markov statistics. For this model, nine
equations are derived that related to the diad and triad
concentrations P.sub.12 and P.sub.21, the probability of propylene
adding to an ethylene-ended chain, and the probability of propylene
adding to a propylene-ended chain, respectively. Thus a fit of
carbon-13 NMR data to these equations yields P.sub.12 and P.sub.21
as the model parameters from which r.sub.1 and r.sub.2 can be
obtained from the relationships: r.sub.1M=(1-P.sub.12)/P.sub.12
r.sub.2/M=(1-P.sub.21)/P.sub.21 The corresponding equations for
random copolymerizations with r.sub.1r.sub.2=1 can also be used to
simplify equation (1), above, to m=r.sub.1M. The ethylene fraction
in the polymer, E, is equal to 1-P.sub.12. This allows the diad and
triad equations to be written in terms of polymer composition:
EE=E.sup.2 EE=2E(1-E) PP=(1-E).sup.2 EEE=E.sup.3 EEP=2E.sup.2(1-E)
EPE=E.sup.2(1-E) PEP=E(1-E).sup.2 PPE=2E(1-E).sup.2
PPP=(1-E).sup.3
Variations and extensions of these equations are provided in the
references incorporated herein, including use of catalysts with
different active sites, equations for estimating the number of
catalyst species present, or complex models such as those with
three or more species present, etc.
From these modeling equations, and those equations presented by
Macromolecules, C. Cozewith et al., entitled "Ethylene-Propylene
Copolymers. Reactivity Ratios, Evaluation, and Significance,"
Volume 4, Issue 4, pp. 482-489, (1971), the average values of
r.sub.1, r.sub.2, and r.sub.1r.sub.2 arising from the
copolymerization kinetics are given by:
r.sub.1=(.SIGMA.r.sub.1if.sub.i/G.sub.i)/(.SIGMA.f.sub.i/G.sub.i)
r.sub.2=(.SIGMA.r.sub.2if.sub.i/G.sub.i)/(.SIGMA.f.sub.i/G.sub.i)
r.sub.1r.sub.2=(.SIGMA.r.sub.1if.sub.i/G.sub.i)(.SIGMA.r.sub.2if.sub.i/G.-
sub.i)/(.SIGMA.f.sub.i/G.sub.i).sup.2 where
G.sub.i=r.sub.1iM.+-.2+r.sub.2i/M These equations and the models
presented in the references cited above may be utilized by those
skilled in the art to characterize the ethylene-based copolymer
composition distribution.
Further information and techniques for measuring intramolecular-CD
are found in Macromolecules, Randell, James C., entitled "Methylene
Sequence Distributions and Number Average Sequence Lengths in
Ethylene-Propylene Copolymers," Volume 11, Issue 1, pp. 33-36,
(1978), Macromolecules, Cheng, H. N., entitled ".sup.13C NMR
Analysis of Ethylene-Propylene Rubbers," Volume 17, Issue 10, pp.
1950-1955, (1984), and Macromolecules, Ray, G. Joseph et al.,
entitled "Carbon-13 Nuclear Magnetic Resonance Determination of
Monomer Composition and Sequence Distributions in
Ethylene-Propylene Copolymers Prepared with a Stereoregular
Catalyst System," Volume 10, Issue 4, pp. 773-778, (1977), each of
which is incorporated by reference in its entirety. Such techniques
are readily known to those skilled in the art of analyzing and
characterizing olefin polymers.
Temperature Rising Elution Fractionation (TREF). The determination
of intermolecular compositional heterogeneity was determined by the
fractionation of the EP copolymer carried out by a Polymer Char
TREF 200 based on a well-known principle that the solubility of a
semi-crystalline copolymer is a strong function of temperature. A
corresponding method is described in U.S. Pat. No. 5,008,204. The
instrument is a column packed with solid stainless-steel beads. The
copolymer of interest was dissolved in 1,2 ortho-dichlorobenzene
(oDCB) at 160.degree. C. for 60 min. Half of a milliliter (ml) of
the polymer solution (concentration=4-5 mg/ml) was injected in the
column and it was stabilized there at 140.degree. C. for 45 min.
The solution was cooled from 140.degree. C. to -15.degree. C. at
1.degree. C./min and equilibrated at this temperature for 10 min.
This caused the copolymer to crystallize out of the quiescent
solution in successive layers of decreasing crystallinity onto the
surface of the beads. Pure solvent (oDCB) was pumped for 5 min at
-15.degree. C. at a flow rate of 1 ml/min through an infrared
detector. A valve was then switched to allow this chilled oDCB to
flow through the column at the same flow rate at -15.degree. C. for
10 min. The material eluted was designated as the soluble fraction
of the copolymer. At this point, the heater was on and the solvent
continued to flow through both the column and the infrared detector
while the temperature was programmed upward at a controlled rate of
2.degree. C./min to 140.degree. C. The infrared detector
continuously measured the concentration of the copolymer in the
effluent from the column, and a continuous solubility distribution
curve was obtained.
EXAMPLES
Example 1
Preparation of The Ethylene Propylene Copolymer of Examples 1 and
2
All polymer compositions in Example 1 were synthesized in one
continuous stirred tank reactors. The polymerization was performed
in solution, using hexane as a solvent. In the reactor,
polymerization was performed at a temperature of 110-115.degree.
C., an overall pressure of 20 bar and ethylene and propylene feed
rates of 1.3 kg/hr and 2 kg/hr, respectively. As catalyst,
N,N-dimethylanilinium tetrakis(pentafluorophenyl)boron was used to
activate
di(p-triethylsilylphenyl)methenyl[(cyclopentadienyl)(2,7-di-tert-butylflu-
orenyl)]hafnium dimethyl. In the process, hydrogen addition and
temperature control were used to achieve the desired MFR. The
catalyst, activated externally to the reactor, was added as needed
in amounts effective to maintain the target polymerization
temperature.
The copolymer solution emerging from the reactor was stopped from
further polymerization by addition of water and then devolatilized
using conventionally known devolatilization methods such as
flashing or liquid phase separation, first by removing the bulk of
the hexane to provide a concentrated solution, and then by
stripping the remainder of the solvent in anhydrous conditions
using a devolatilizer or a twin screw devolatilizing extruder so as
to end up with a molten polymer composition containing less than
0.5 wt % of solvent and other volatiles. The molten polymer was
cooled until solid.
The composition, melt viscosity and molecular weight properties of
the ethylene copolymers of Example 1 are shown in Table I.
TABLE-US-00001 TABLE 1 Melt viscosity GPC Composition (dg/10 m) Mw
Ethylene MFR @ 230.degree. C. (kg/mol) Example Wt % 2.16 Kg 21.6 Kg
Kg/mol Mw/Mn 1-A 63.6 9.2 175 82 1.84 1-B 70.5 13 238 71 1.85 1-C
59.0 15 280 75 1.81 1-D 69.2 12 239 71 1.87 1-E 62.3 12 259 76 1.93
1-F 74.2 15 277 69 1.90 1-G 57.3 8.0 184 89 1.94 1-H 60.7 7.9 159
91 1.82
The temperature of melting data and heat of fusion for the ethylene
copolymers of Example 1 are shown in Table 2.
TABLE-US-00002 TABLE 2 DSC 1.sup.st melt 2.sup.nd cool 2.sup.nd
melt Melting Heat of Crystallization Heat of Melting Heat of Temp
(T.sub.m) Fusion (H.sub.f) Temp (T.sub.c) Fusion (H.sub.f) Temp
(T.sub.m) Fusion (H.sub.f) Example .degree. C. J/g .degree. C. J/g
.degree. C. J/g 1-A 3.2 26 -2.0 29 -2.5 27 1-B 24, 46 38 14 41 31
33 1-C -13 21 -16 21 -14 17 1-D 23, 44 41 13 43 27 41 1-E -3.0 28
-5.7 22 -4.3 23 1-F 21, 48 54 18, 26 49 37 48 1-G -15 18 -18 20 -17
21 1-H -9.4 21 -13 23 -11 25
TABLE-US-00003 TABLE 3 SSI (KO-30 pass)* Example TE* (%) 1-C 1.92
17.86 1-D 2.02 15.23 1-E 1.99 18.26 1-F 1.97 14.14 1-G 2.11 23.32
1-H 2.15 23.4
The TE* and SSI* values in Table 3 were measured for a 1 wt. %
polymer concentration of the ethylene copolymers of Example 1 in a
Americas Core 150 using an ExxonMobil Group I basestock stock with
the following lubricant properties: ASTM D445-5, Kinematic
viscosity @100.degree. C.=5.189 cSt; ASTM D445-3, Kinematic
viscosity @40.degree. C.=29 cSt min.; ASTM D2270 Viscosity index=95
min.; ASTM D92 Flash point COC=210.degree. C. min.; ASTM D97 Pour
point=-15.degree. C. max.; and ASTM D5800 Noack volatility=20 wt %
max.
Example 2
Table 4 shows the compositionally disperse and crystallinity
disperse blends of the ethylene copolymers of Example 1. These
disperse blends were made by melt blended, in multiple batches
using aliquots of different polymers, at a temperature of
120.degree. C. to 150.degree. C. for 3 to 5 minutes in an Brabender
mixer having an internal cavity of 250 ml using low shear blades
rotating at speed of 15 to 20 rpm. The ethylene copolymers were
protected during the mixing operation by having a nitrogen blanket
and by the addition of 1000 ppm of a 3:1 mixture of Irganox 1076
and Irgafos 168 before mixing.
TABLE-US-00004 TABLE 4 Ethylene Copolymers used to Make
Compositionally Disperse and Crystallinity Disperse Polymeric
Blends (Parts of Each Copolymer) Example Example Example Example
Example Example Example Example Example No 1-A 1-B 1-C 1-D 1-E 1-F
1-G 1-H 2-A 210 90 2-B 90 210 2-C 240 60 2-D 210 90 2-E 240 60 2-F
210 90 2-G 240 60 2-H 210 90 2-I 90 210 2-J 90 210 2-K 210 90 2-L
90 210 2-M 90 210 2-N 90 210 2-O 90 210 2-P 60 240 2-Q 90 210 2-R
120 180 2-S 60 240 2-T 90 210 2-U 210 90 2-V 180 120 2-W 180 120
2-X 180 120 2-Y 60 240 2-Z 120 180 2-Z1 120 180
The properties of the compositionally and crystallinity disperse
blends made in Example 2 are shown in Table 5.
TABLE-US-00005 TABLE 5 Melt viscosity GPC (dg/10 m) Mw Example
Composition MFR @ 230.degree. C. (kg/mol) No. Wt. % C2 2.16 Kg 21.6
Kg kg/mol Mw/Mn 2-A 62.5 13 244 76 1.84 2-B 63.2 14 275 73 1.82 2-C
65.5 9.5 210 80 1.9 2-D 65.6 9.6 211 78 1.93 2-E 65.0 9.7 198 78
1.90 2-F 65.5 10 219 79 1.86 2-G 64.7 13 261 74 1.89 2-H 65.9 13
258 76 1.88 2-I 64.2 11 257 76 1.89 2-J 64.4 13 245 75 1.87 2-K
65.5 76 1.93 2-L 63.4 9.0 182 83 1.93 2-M 63.6 8.6 181 81 1.96 2-N
59.7 8.4 185 86 1.85 2-O 61.8 8.6 184 84 1.93 2-P 60.3 8.6 185 86
1.90 2-Q 62.1 9.5 195 83 1.99 2-R 63.0 82 1.99 2-S 60.7 8.9 195 83
1.93 2-T 62.7 11 216 80 1.97
The temperature of melting and heat of fusion for the
compositionally and crystallinity disperse blends of Example 2 are
shown in Table 6.
TABLE-US-00006 TABLE 6 DSC 1.sup.st melt 2.sup.nd cool 2.sup.nd
melt Heat Crystalli- Heat of Heat of Ex- Melting of Fusion zation
Fusion Melting Fusion ample Temp (H.sub.f) Temp (T.sub.c) (H.sub.f)
Temp (H.sub.f) No. (T.sub.m) .degree. C. J/g .degree. C. J/g
(T.sub.m) .degree. C. J/g 2-A 2.6, 51 33 3.7, -18 25 33, -4.6 37
2-B 5.4, 47 21 7.9, -20 26 31, -3.7 17 2-C 11, 46 30 -2.9 28 4.5 27
2-D 14, 46 32 0.6 31 6.7 35 2-E 13, 46 22 -2.8 33 4.1 22 2-F 16, 46
23 -1.2 37 8.0 27 2-G 11, 46 32 17, -7.6 31 2.5 27 2-H 14, 46 32
20, -7.7 31 6.6, 48 32 2-I 9.3, 47 29 -3.9 34 2.7 32 2-J 13, 45 39
-6.4 40 -3.3 28 2-K 14, 47 29 19, -10 32 4.6, 48 31 2-L 2.2, 45 36
-12 36 -2.9 25 2-M 5.9, 46 27 8.7, -14 29 44, -2.3 24 2-N 48, -7.1
26 3.9, -23 23 42, -12 22 2-O 1.2, 48 24 4.7, -21 23 36, -6.2 22
2-P 47, -8.0 26 6.5, -23 25 37, -11 22 2-Q 2.0, 46 20 8.7, -23 26
41, -6.2 23 2-R 20, 45 24 8.2, -23 33 33, -4.5 29 2-S 45, -7.1 16
18, -23 22 44, -11 25 2-T 2.5, 46 29 20, -22 30 45, -6.2 30
TABLE-US-00007 TABLE 7 SSI* SSI* Example (KO-30 Pass) (KO-90 Pass)
No. (%) (%) TE* 2-A 10.43 13.71 1.71 2-B 8.89 12.15 1.72 2-C 14.72
18.26 1.73 2-D 14.75 18.43 1.78 2-E 16.01 20.07 1.93 2-F 15.17
19.21 1.93 2-G 12.81 16.30 1.74 2-H 11.85 15.70 1.72 2-I 12.16
15.55 1.78 2-J 11.68 15.76 1.74 2-K 11.45 15.27 1.73 2-L 16.06
20.34 1.85 2-M 17.32 21.10 1.84 2-N 15.65 19.70 1.84 2-O 17.18
21.20 1.85 2-P 16.23 20.29 1.84 2-Q 17.46 21.00 1.83 2-R 16.00
19.31 1.81 2-S 16.95 20.72 1.84 2-T 11.73 15.28 1.83
The SSI* and TE* values in Table 7 were measured for a 1 wt. %
polymer concentration of the compositionally and crystallinity
disperse blends of Example 2 in PAO-4 which is an ExxonMobil
Chemical synthetic basestock stock (SpectraSyn) with the following
lubricant properties: ASTM D445-5 Kinematic viscosity @100.degree.
C.=4.14 cSt; ASTM D445-3 Kinematic viscosity @40.degree. C.=19 cSt;
ASTM D2270 Viscosity index=126; ASTM D92 Flash point COC=220 C min;
ASTM D97 Pour point=-66.degree. C.; and ASTM D1298 Specific gravity
@15.6/15.6.degree. C.=0.820.
TABLE-US-00008 TABLE 8 SSI* SSI* Example (KO-30 Pass) (KO-90 Pass)
No. (%) (%) TE* 2-A 17.56 21.55 1.95 2-B 18.41 22.57 1.96 2-C 21.55
26.44 2.09 2-D 21.36 26.75 2.10 2-E 20.32 25.31 2.12 2-F 18.87
23.59 2.09 2-G 18.46 23.57 1.97 2-H 17.02 21.91 1.98 2-I 19.13
24.05 2.03 2-J 16.34 20.67 1.70 2-K 16.34 20.23 1.99 2-L 20.00
24.81 2.06 2-M 22.67 27.32 2.11 2-N 23.28 28.33 2.10 2-O 22.40
27.41 2.11 2-P 23.44 28.24 2.12 2-Q 22.38 26.89 2.10 2-R 20.81
25.65 2.05 2-S 22.51 28.36 2.12 2-T 21.13 26.04 2.08
The SSI** and TE** values in Table 8 were measured for a 1 wt. %
polymer concentration of the compositionally and crystallinity
disperse blends of Example 2 in an Americas Core 150 which is
ExxonMobil Group I basestock with the following lubricant
properties: ASTM D445-5, Kinematic viscosity @100.degree. C.=5.189
cSt; ASTM D445-3, Kinematic viscosity @40.degree. C.=29 cSt min.;
ASTM D2270 Viscosity index=95 min.; ASTM D92 Flash point
COC=210.degree. C. min.; ASTM D97 Pour point=-15.degree. C. max.;
and ASTM D5800, Noack volatility=20 wt. % max.
The samples of compositionally and crystallinity disperse blends
were dissolved in PAO-4 at a concentration of 2.5 wt. % and
rheologically tested on the Anton-Parr rheometer as described above
at a temperature of 20.degree. C. to -35.degree. C. The complex
viscosity data for the disperse blends and a comparative
Ziegler-Natta-based polymeric compositions are shown in Tables
9-13. The complex viscosity data for the disperse blends and a
metallocene-based polymeric composition is displayed as a function
of temperature in FIG. 1.
TABLE-US-00009 TABLE 9 Example 2-A Example 2-B Example 2-C Example
2-D Complex Complex Complex Complex T Viscosity T Viscosity T
Viscosity T Viscosity C [Pa s] C [Pa s] C [Pa s] C [Pa s] 20.00
1.51 20.00 0.31 20.00 0.44 20.00 0.88 18.20 0.33 18.20 0.13 18.20
0.44 18.30 0.78 16.60 0.45 16.60 0.26 16.60 0.37 16.60 0.42 15.00
0.56 15.00 0.09 15.10 0.45 15.10 0.39 13.40 0.33 13.50 0.48 13.50
0.28 13.40 0.57 11.80 0.46 11.90 0.46 11.90 0.41 11.90 0.91 10.30
0.34 10.30 0.44 10.30 0.33 10.30 0.52 8.62 0.56 8.73 0.29 8.70 0.27
8.72 0.90 7.09 0.85 7.11 0.41 7.14 0.49 7.11 0.84 5.54 0.46 5.56
0.63 5.54 0.74 5.55 0.77 4.09 0.81 3.96 0.38 3.98 0.67 3.96 0.60
2.33 0.89 2.36 0.28 2.43 0.79 2.37 0.77 0.91 0.69 0.84 0.73 0.81
0.86 0.86 1.02 -0.77 0.66 -0.82 1.04 -0.78 0.59 -0.76 0.65 -2.39
0.67 -2.40 0.66 -2.35 0.85 -2.44 0.88 -3.96 0.76 -3.92 1.43 -3.91
0.86 -3.94 0.86 -5.42 0.78 -5.51 0.82 -5.52 0.93 -5.50 1.11 -7.06
1.12 -7.07 0.94 -7.14 0.80 -7.14 0.81 -8.79 1.10 -8.69 1.08 -8.64
1.14 -8.69 1.14 -10.20 1.54 -10.20 1.28 -10.30 0.99 -10.30 1.53
-11.80 1.53 -11.90 1.68 -11.90 1.37 -11.80 1.33 -13.40 1.91 -13.40
1.49 -13.40 1.49 -13.50 1.62 -15.10 1.89 -15.00 1.78 -15.10 1.81
-15.10 1.87 -16.60 2.24 -16.60 2.05 -16.60 1.45 -16.70 2.01 -18.20
2.71 -18.20 2.63 -18.20 2.03 -18.10 2.38 -19.70 3.04 -19.70 2.54
-19.80 1.99 -19.90 3.04 -21.30 3.53 -21.40 2.94 -21.30 2.56 -21.30
3.14 -22.90 3.71 -22.90 3.53 -22.90 2.75 -23.00 3.48 -24.40 4.38
-24.40 3.80 -24.50 3.40 -24.50 3.90 -26.20 4.71 -26.10 4.51 -26.20
4.22 -26.10 4.98 -27.70 5.61 -27.70 4.95 -27.70 5.69 -27.70 6.70
-29.20 6.18 -29.20 5.82 -29.20 8.58 -29.20 9.17 -30.80 7.14 -30.90
6.30 -30.80 13.00 -30.90 13.40 -32.40 8.10 -32.40 7.67 -32.40 23.10
-32.40 16.60 -34.00 9.39 -34.00 8.70 -34.00 39.70 -34.00 31.40
-35.10 10.50 -35.20 10.10 -35.20 62.80 -35.20 38.00
TABLE-US-00010 TABLE 10 Example 2-E Example 2-F Example 2-G Example
2-H Complex Complex Complex Complex T Viscosity T Viscosity T
Viscosity T Viscosity C [Pa s] C [Pa s] C [Pa s] C [Pa s] 20.00
0.26 20.00 0.80 20.00 0.78 20.00 0.94 18.20 0.43 18.30 0.75 18.30
0.30 18.30 0.26 16.70 0.44 16.60 0.27 16.70 0.68 16.60 0.29 15.00
0.35 15.10 0.41 15.00 0.43 15.10 0.26 13.50 0.69 13.40 0.41 13.40
0.30 13.50 0.62 11.90 0.45 11.90 0.54 11.90 0.58 11.90 0.61 10.30
0.65 10.30 0.63 10.30 0.60 10.30 0.34 8.73 0.15 8.74 0.37 8.67 0.39
8.72 0.44 7.17 0.52 7.16 0.59 7.08 0.64 7.24 0.56 5.58 1.32 5.59
0.52 5.60 0.55 5.56 0.42 3.98 0.82 3.91 0.90 3.92 0.77 4.00 0.72
2.44 0.73 2.36 0.62 2.40 0.79 2.40 0.90 0.77 0.73 0.78 0.60 0.82
0.68 0.82 0.61 -0.80 0.93 -0.79 0.94 -0.79 0.65 -0.76 0.81 -2.24
0.78 -2.37 1.10 -2.30 0.37 -2.35 0.84 -3.97 0.85 -3.97 1.16 -3.92
0.85 -3.92 1.14 -5.51 0.92 -5.55 1.06 -5.51 1.09 -5.54 1.09 -7.08
1.28 -7.07 1.13 -7.12 0.82 -7.09 1.33 -8.72 1.12 -8.69 1.31 -8.69
0.95 -8.71 1.27 -10.30 1.22 -10.40 1.42 -10.30 0.91 -10.20 1.32
-11.90 1.52 -11.80 1.66 -11.80 1.34 -11.90 1.84 -13.50 1.88 -13.40
1.71 -13.40 1.40 -13.50 2.13 -15.00 1.75 -15.00 1.87 -15.00 1.77
-15.00 2.05 -16.60 2.05 -16.60 2.12 -16.60 1.92 -16.60 2.30 -18.20
2.23 -18.20 2.58 -18.20 1.92 -18.10 2.54 -19.70 2.44 -19.90 2.84
-19.70 2.25 -19.80 2.86 -21.30 2.60 -21.30 3.20 -21.40 2.65 -21.30
3.41 -22.90 3.30 -22.90 3.67 -22.90 2.87 -22.90 3.69 -24.50 3.76
-24.50 4.22 -24.50 3.22 -24.50 4.30 -26.00 5.17 -26.00 5.14 -26.10
3.63 -26.00 4.85 -27.70 7.15 -27.70 6.46 -27.70 4.51 -27.70 6.04
-29.40 11.20 -29.40 8.99 -29.30 6.19 -29.30 7.26 -30.80 21.30
-30.80 12.40 -30.90 9.09 -30.80 9.45 -32.40 33.10 -32.40 16.70
-32.40 14.80 -32.40 11.60 -34.00 71.70 -34.00 28.70 -34.10 27.30
-34.00 15.30 -35.20 102.00 -35.20 38.90 -35.10 41.80 -35.20
21.30
TABLE-US-00011 TABLE 11 Example 2-I Example 2-J Example 2-K*
Example 2-L Complex Complex Complex Complex T Viscosity T Viscosity
T Viscosity T Viscosity C [Pa s] C [Pa s] C [Pa s] C [Pa s] 20.00
1.80 20.00 0.31 20.00 0.17 20.00 1.75 18.20 0.52 18.30 0.19 18.20
0.05 18.30 0.40 16.60 0.20 16.60 0.36 16.60 0.14 16.60 0.91 15.10
0.41 15.10 0.36 15.10 0.18 15.10 0.15 13.50 0.46 13.50 0.41 13.40
0.23 13.40 0.66 11.80 0.12 11.90 0.49 11.90 0.34 11.90 0.48 10.30
0.51 10.30 0.76 10.30 0.21 10.30 0.51 8.75 0.39 8.73 0.30 8.73 0.18
8.70 0.62 7.12 0.59 7.16 0.41 7.11 0.24 7.11 0.66 5.49 0.92 5.57
0.77 5.54 0.37 5.54 0.48 3.98 0.87 3.92 0.51 3.93 0.25 3.99 0.58
2.40 0.72 2.41 0.39 2.27 0.46 2.36 0.64 0.80 0.74 0.79 0.71 0.82
0.39 0.83 0.91 -0.78 0.51 -0.76 0.79 -0.76 0.19 -0.78 0.63 -2.29
0.81 -2.37 0.75 -2.41 0.37 -2.35 0.92 -3.91 0.72 -3.91 0.67 -4.05
0.54 -3.89 0.76 -5.61 0.78 -5.50 0.94 -5.49 0.39 -5.41 1.28 -7.12
0.97 -7.10 1.00 -7.08 0.36 -7.14 1.02 -8.60 0.72 -8.73 1.11 -8.68
0.54 -8.72 1.30 -10.30 1.36 -10.30 1.61 -10.30 0.45 -10.30 1.49
-11.90 1.58 -11.90 1.37 -11.90 0.57 -11.90 1.53 -13.50 1.77 -13.40
1.63 -13.40 0.42 -13.40 2.20 -15.10 1.78 -15.00 1.98 -15.00 0.73
-15.00 2.09 -16.60 1.80 -16.50 2.38 -16.70 0.40 -16.60 2.46 -18.20
2.28 -18.20 2.30 -18.20 0.64 -18.10 2.74 -19.70 2.46 -19.70 2.44
-19.70 0.80 -19.80 3.12 -21.40 2.87 -21.30 2.83 -21.30 0.83 -21.40
3.66 -22.90 3.00 -22.90 3.38 -23.00 0.99 -23.00 4.02 -24.50 3.27
-24.50 3.89 -24.50 1.07 -24.40 4.49 -26.10 3.94 -26.10 4.42 -26.10
1.26 -26.10 5.01 -27.70 4.37 -27.70 4.75 -27.70 1.29 -27.60 5.61
-29.30 5.14 -29.20 6.19 -29.30 1.42 -29.20 6.59 -30.90 6.14 -30.70
7.04 -30.80 1.57 -30.80 7.53 -32.40 7.81 -32.40 9.04 -32.40 1.75
-32.40 8.50 -34.00 10.80 -34.00 12.20 -34.00 2.13 -34.10 9.67
-35.20 12.80 -35.20 16.10 -35.10 2.19 -35.20 11.50 *Complex
viscosity measured for a 1.0 wt. % concentration in PAO-4.
TABLE-US-00012 TABLE 12 Example 2-M Example 2-N Example 2-O Example
2-P Complex Complex Complex Complex T Viscosity T Viscosity T
Viscosity T Viscosity C [Pa s] C [Pa s] C [Pa s] C [Pa s] 20.00
0.16 20.00 0.63 19.90 0.75 20.10 0.50 18.30 0.22 18.20 0.52 18.20
0.16 18.20 0.42 16.70 0.11 16.60 0.22 16.60 0.47 16.70 0.41 14.90
0.68 15.00 0.57 15.10 0.30 15.10 0.32 13.60 0.58 13.40 0.61 13.50
0.41 13.40 0.89 11.90 0.83 11.90 0.39 11.80 0.37 11.90 0.40 10.20
0.35 10.30 0.52 10.40 0.81 10.20 0.39 8.71 0.55 8.69 0.51 8.74 0.32
8.69 0.35 7.15 0.49 7.19 0.71 7.14 0.48 7.07 0.28 5.52 0.79 5.52
0.83 5.53 0.74 5.60 0.76 4.00 0.48 4.03 0.79 3.99 0.55 3.89 0.62
2.38 0.77 2.37 0.93 2.37 0.52 2.32 0.64 0.80 0.55 0.76 1.00 0.85
0.74 0.78 0.58 -0.85 0.83 -0.78 0.81 -0.78 0.94 -0.73 0.47 -2.37
0.93 -2.37 1.01 -2.38 0.62 -2.46 1.05 -3.93 1.25 -3.95 1.05 -3.97
0.94 -3.97 1.19 -5.52 1.41 -5.57 0.75 -5.59 0.92 -5.55 1.12 -7.11
1.34 -7.09 1.06 -7.13 1.09 -7.07 1.27 -8.72 1.57 -8.69 1.05 -8.66
1.39 -8.73 1.48 -10.30 1.78 -10.30 1.50 -10.30 1.80 -10.30 1.40
-11.90 1.88 -11.90 1.82 -11.90 1.66 -11.90 1.65 -13.40 2.09 -13.50
1.79 -13.50 1.91 -13.50 1.92 -15.00 2.40 -15.00 1.90 -15.00 1.98
-15.00 2.14 -16.60 2.50 -16.60 2.21 -16.50 2.42 -16.60 2.35 -18.20
2.73 -18.20 2.58 -18.20 2.61 -18.20 2.62 -19.80 3.15 -19.70 2.88
-19.70 2.94 -19.70 2.86 -21.30 3.72 -21.40 3.27 -21.40 3.69 -21.40
3.48 -22.90 4.03 -23.00 3.66 -23.00 3.68 -22.90 3.87 -24.50 4.83
-24.50 4.15 -24.50 4.35 -24.50 4.14 -26.10 5.41 -26.20 4.88 -26.10
4.98 -26.10 4.99 -27.70 6.24 -28.50 6.22 -27.70 5.52 -27.70 5.70
-29.30 7.19 -29.20 6.37 -29.30 6.51 -29.30 6.65 -30.80 7.98 -30.70
7.30 -30.80 7.23 -30.80 7.79 -32.40 9.33 -32.30 8.32 -32.40 8.43
-32.40 8.91 -34.10 10.70 -34.00 9.75 -34.00 10.10 -34.00 10.10
-35.20 12.70 -35.20 11.30 -35.20 11.20 -35.20 11.70
TABLE-US-00013 TABLE 13 Ziegler-Natta- based Example 2-Q Example
2-R* Example 2-S Example 2-T Comparative Complex Complex Complex
Complex Complex T Viscosity T Viscosity T Viscosity T Viscosity T
Viscosity C [Pa s] C [Pa s] C [Pa s] C [Pa s] C [Pa s] 20.00 1.51
20.00 1.99 20.10 0.35 20.10 1.85 20.10 0.14 18.20 0.66 18.20 0.56
18.20 0.42 18.30 0.03 18.30 0.30 16.70 0.22 16.60 0.38 16.70 0.43
16.60 0.34 16.60 0.41 15.00 0.52 15.10 0.21 15.10 0.41 15.10 0.36
15.00 0.21 13.50 0.30 13.50 0.63 13.50 0.44 13.40 0.37 13.50 0.48
11.70 0.49 11.90 0.22 11.90 0.68 11.90 0.29 11.90 0.70 10.40 0.67
10.30 0.23 10.30 0.36 10.20 0.47 10.30 0.52 8.76 0.49 8.75 0.28
8.76 0.33 8.69 0.31 8.76 0.47 7.08 0.68 7.14 0.23 7.16 0.45 7.17
0.51 7.17 0.59 5.57 0.72 5.57 0.16 5.52 0.69 5.54 0.69 5.56 0.69
3.96 0.85 3.97 0.37 4.00 0.56 4.06 0.86 3.94 0.70 2.36 0.55 2.40
0.15 2.40 0.59 2.44 1.25 2.39 0.60 0.77 0.70 0.75 0.18 0.83 0.66
0.85 1.38 0.77 1.15 -0.79 1.06 -0.75 0.50 -0.74 1.03 -0.85 1.26
-0.76 1.01 -2.43 0.77 -2.39 0.28 -2.41 0.91 -2.33 1.37 -2.26 1.07
-4.03 1.10 -3.90 0.37 -3.89 1.02 -3.91 1.71 -4.01 1.52 -5.49 1.31
-5.51 0.42 -5.50 0.99 -5.52 1.78 -5.50 1.71 -7.10 1.59 -7.19 0.21
-7.07 1.29 -7.11 1.95 -7.09 1.74 -8.67 1.59 -8.67 0.60 -8.72 1.49
-8.69 1.98 -8.74 1.86 -10.30 1.93 -10.30 0.39 -10.20 1.49 -10.30
2.41 -10.20 2.60 -11.80 2.05 -11.90 0.49 -11.90 1.80 -11.90 2.49
-11.90 2.87 -13.50 2.37 -13.40 0.49 -13.50 2.12 -13.40 3.07 -13.40
3.20 -14.90 2.41 -15.10 0.48 -15.00 2.25 -15.10 3.24 -15.00 4.24
-16.60 2.75 -16.60 0.49 -16.60 2.51 -16.60 3.28 -16.60 4.61 -18.10
3.10 -18.30 0.80 -18.20 2.81 -18.20 3.73 -18.20 5.47 -19.70 3.48
-19.80 0.87 -19.80 3.27 -19.70 4.50 -19.80 7.11 -21.40 3.84 -21.40
0.85 -21.40 3.75 -21.40 4.93 -21.30 7.93 -23.00 4.44 -23.00 0.99
-22.90 4.14 -22.90 5.60 -22.90 8.41 -24.50 4.96 -24.50 1.09 -24.50
4.93 -24.60 6.15 -24.60 10.00 -26.00 5.70 -26.00 1.34 -26.20 5.54
-26.10 7.15 -26.10 11.40 -27.60 6.64 -27.60 1.53 -27.70 6.27 -27.70
8.09 -27.70 13.90 -29.20 7.31 -29.20 1.48 -29.30 7.09 -29.40 9.43
-29.20 14.80 -30.90 8.84 -30.80 2.05 -30.90 8.40 -30.80 10.70
-30.80 17.40 -32.40 9.76 -32.40 2.28 -32.40 9.83 -32.40 11.90
-32.40 18.20 -34.00 11.60 -33.90 2.80 -34.00 11.30 -34.00 13.60
-34.00 20.80 -35.20 12.80 -35.20 2.88 -35.20 12.80 -35.20 16.00
-35.10 24.30 *Complex viscosity measured for a 1.0 wt. %
concentration in PAO-4.
The samples of compositionally disperse and crystallinity disperse
blends and a Ziegler-Natta-based polymeric composition were also
investigated for shear stress and strain as shown in Tables
14-18.
Shear stress as a function of strain for the disperse blends and a
metallocene-based polymeric composition is displayed in FIG. 2.
TABLE-US-00014 TABLE 14 Example 2-A Example 2-B Example 2-C Example
2-D Shear Shear Shear Shear Strain Stress Strain Stress Strain
Stress Strain Stress [%] [Pa] [%] [Pa] [%] [Pa] [%] [Pa] 0.0679
0.01 0.0785 0.02 0.0844 0.01 0.0723 0.02 0.586 0.02 0.602 0.01
0.601 0.01 0.598 0.01 1.42 0.02 1.43 0.02 1.43 0.02 1.44 0.01 2.75
0.02 2.76 0.03 2.76 0.02 2.76 0.02 5.57 0.04 5.59 0.03 5.58 0.04
5.59 0.02 9.37 0.04 9.38 0.05 9.38 0.05 9.37 0.05 15.4 0.06 15.4
0.06 15.4 0.07 15.4 0.08 25.1 0.09 25.1 0.09 25.1 0.12 25.1 0.12
40.5 0.13 40.5 0.12 40.5 0.18 40.5 0.19 65 0.19 65 0.16 65 0.29 65
0.30 104 0.26 104 0.24 104 0.47 104 0.52 167 0.43 167 0.37 166 0.88
166 0.91 266 0.65 266 0.57 266 1.64 266 1.34 424 1.00 424 0.91 424
2.51 424 1.74 677 1.52 677 1.37 677 3.01 677 2.22 1,080 2.26 1,080
2.01 1,080 3.54 1,080 2.90 1,720 3.35 1,720 3.04 1,720 4.49 1,720
3.86 2,750 5.08 2,750 4.63 2,750 6.27 2,750 5.39 4,380 7.84 4,380
7.19 4,380 8.87 4,380 7.73 6,980 12.20 6,980 11.20 6,980 12.60
6,980 11.20 7,840 13.50 7,840 12.5 7,840 13.80 7,840 12.30 8,810
15.10 8,810 13.9 8,810 15.10 8,810 13.50
TABLE-US-00015 TABLE 15 Example 2-E Example 2-F Example 2-G Example
2-H Shear Shear Shear Shear Strain Stress Strain Stress Strain
Stress Strain Stress [%] [Pa] [%] [Pa] [%] [Pa] [%] [Pa] 0.0805
0.00 0.0792 -0.01 0.0708 0.02 0.0773 0.01 0.597 0.01 0.588 0.00
0.597 0.02 0.603 0.01 1.43 0.01 1.42 0.01 1.43 0.03 1.43 0.02 2.76
0.02 2.75 0.01 2.76 0.03 2.76 0.02 5.58 0.03 5.55 0.04 5.57 0.04
5.58 0.03 9.36 0.06 9.35 0.05 9.37 0.06 9.38 0.05 15.4 0.09 15.4
0.07 15.4 0.08 15.4 0.07 25.1 0.15 25.1 0.11 25.1 0.12 25.1 0.11
40.4 0.24 40.4 0.17 40.5 0.17 40.5 0.18 65 0.39 65 0.28 65 0.24 65
0.27 104 0.69 104 0.51 104 0.36 104 0.41 166 1.27 166 0.84 166 0.55
166 0.65 266 2.40 266 1.23 266 0.86 266 0.94 424 3.45 424 1.65 424
1.28 424 1.31 677 3.90 677 2.15 677 1.90 677 1.81 1,080 4.36 1,080
2.84 1,080 2.73 1,080 2.59 1,720 5.37 1,720 3.92 1,720 3.92 1,720
3.70 2,750 7.35 2,750 5.51 2,750 5.72 2,750 5.32 4,380 10.30 4,380
7.84 4,380 8.43 4,380 7.72 6,980 14.60 6,980 11.30 6,980 12.50
6,980 11.30 7,840 15.90 7,840 12.50 7,840 13.80 7,840 12.5 8,810
17.30 8,810 13.70 8,810 15.20 8,810 13.8
TABLE-US-00016 TABLE 16 Example 2-I Example 2-J Example 2-K*
Example 2-L Shear Shear Shear Shear Strain Stress Strain Stress
Strain Stress Strain Stress [%] [Pa] [%] [Pa] [%] [Pa] [%] [Pa]
0.0703 -0.01 0.072 0.00 0.0673 0.02 0.0657 0.01 0.593 0.00 0.595
0.00 0.594 0.01 0.589 0.01 1.42 0.01 1.43 0.01 1.43 0.01 1.42 0.03
2.75 0.02 2.76 0.01 2.76 0.02 2.75 0.02 5.57 0.01 5.57 0.03 5.59
0.02 5.57 0.03 9.37 0.03 9.37 0.04 9.39 0.01 9.37 0.05 15.4 0.05
15.4 0.06 15.5 0.02 15.4 0.06 25.1 0.07 25.1 0.09 25.1 0.03 25.1
0.09 40.5 0.12 40.5 0.13 40.5 0.03 40.5 0.12 65 0.19 65 0.21 65.1
0.04 65 0.20 104 0.29 104 0.33 104 0.08 104 0.29 166 0.41 166 0.50
167 0.10 166 0.47 266 0.65 266 0.79 266 0.16 266 0.73 424 1.00 424
1.14 425 0.25 424 1.11 677 1.44 677 1.64 677 0.38 677 1.68 1,080
2.13 1,080 2.41 1,080 0.60 1,080 2.55 1,720 3.16 1,720 3.53 1,720
0.94 1,720 3.85 2,750 4.77 2,750 5.22 2,750 1.47 2,750 5.94 4,380
7.14 4,380 7.81 4,380 2.31 4,380 9.16 6,980 10.90 6,980 11.70 6,980
3.69 6,980 14.20 7,840 12.00 7,840 13.00 7,850 4.15 7,840 15.80
8,810 13.40 8,810 14.40 8,820 4.64 8,810 17.70 *Shear stress and
strain measured for a 1.0 wt. % concentration in PAO-4.
TABLE-US-00017 TABLE 17 Example 2-M Example 2-N Example 2-O Example
2-P Shear Shear Shear Shear Strain Stress Strain Stress Strain
Stress Strain Stress [%] [Pa] [%] [Pa] [%] [Pa] [%] [Pa] 0.0758
0.02 0.0752 0.00 0.0683 0.03 0.0673 0.02 0.593 0.03 0.59 0.02 0.596
0.02 0.584 0.03 1.42 0.04 1.43 0.02 1.43 0.02 1.42 0.03 2.75 0.04
2.76 0.02 2.76 0.03 2.75 0.03 5.58 0.05 5.58 0.03 5.58 0.04 5.58
0.03 9.37 0.06 9.38 0.04 9.38 0.06 9.37 0.05 15.4 0.08 15.4 0.05
15.4 0.08 15.4 0.07 25.1 0.10 25.1 0.08 25.1 0.09 25.1 0.09 40.5
0.15 40.5 0.10 40.5 0.14 40.5 0.13 65 0.23 65 0.15 65 0.19 65 0.17
104 0.34 104 0.25 104 0.29 104 0.28 166 0.52 167 0.39 167 0.41 167
0.41 266 0.80 266 0.61 266 0.67 266 0.64 424 1.22 424 0.97 424 1.03
424 0.97 677 1.87 677 1.53 677 1.57 677 1.51 1,080 2.80 1,080 2.39
1,080 2.36 1,080 2.38 1,720 4.13 1,720 3.77 1,720 3.60 1,720 3.72
2,750 6.17 2,750 5.98 2,750 5.54 2,750 5.82 4,380 9.48 4,380 9.41
4,380 8.60 4,380 9.19 6,980 14.60 6,980 14.90 6,980 13.40 6,980
14.40 7,840 16.30 7,840 16.7 7,840 14.90 7,840 16.20 8,810 18.10
8,810 18.7 8,810 16.70 8,810 18.10
TABLE-US-00018 TABLE 18 Ziegler-Natta- based Example 2-Q Example
2-R* Example 2-S Example 2-T Comparative Shear Shear Shear Shear
Shear Strain Stress Strain Stress Strain Stress Strain Stress
Strain Stress [%] [Pa] [%] [Pa] [%] [Pa] [%] [Pa] [%] [Pa] 0.0755
0.01 0.0625 0.02 0.0743 0.01 0.0756 0.01 0.0741 0.00 0.594 0.01
0.589 0.02 0.592 0.02 0.61 0.00 0.598 0.00 1.43 0.00 1.42 0.03 1.42
0.03 1.44 0.01 1.42 0.02 2.76 0.01 2.75 0.04 2.76 0.03 2.76 0.01
2.75 0.02 5.58 0.02 5.58 0.02 5.58 0.03 5.58 0.03 5.57 0.03 9.38
0.02 9.38 0.03 9.37 0.05 9.37 0.05 9.36 0.05 15.4 0.05 15.4 0.04
15.4 0.06 15.4 0.06 15.4 0.09 25.1 0.09 25.1 0.03 25.1 0.10 25.1
0.11 25.1 0.14 40.5 0.13 40.5 0.04 40.5 0.12 40.5 0.16 40.4 0.22 65
0.19 65.1 0.06 65 0.19 65 0.24 65 0.37 104 0.30 104 0.09 104 0.28
104 0.39 104 0.66 166 0.49 167 0.15 167 0.46 166 0.61 166 1.28 266
0.74 266 0.18 266 0.71 266 0.99 266 2.21 424 1.17 425 0.28 424 1.08
424 1.50 424 2.89 677 1.79 677 0.44 677 1.64 677 2.15 677 3.28
1,080 2.63 1,080 0.68 1,080 2.54 1,080 3.06 1,080 3.86 1,720 3.91
1,720 1.04 1,720 3.92 1,720 4.33 1,720 4.97 2,750 5.92 2,750 1.68
2,750 6.08 2,750 6.24 2,750 6.83 4,380 9.12 4,380 2.61 4,380 9.49
4,380 9.29 4,380 9.59 6,980 14.10 6,980 4.11 6,980 14.80 6,980
14.10 6,980 13.70 7,840 15.70 7,850 4.61 7,840 16.60 7,840 15.70
7,840 15.00 8,810 17.60 8,820 5.19 8,810 18.50 8,810 17.50 8,810
16.40 *Shear stress and strain measured for a 1.0 wt. %
concentration in PAO-4.
These above data demonstrate that polymer compositions of the
present invention can be processed into lubricant formulations
having properties similar to those of formulations made from
components prepared by more complex and more expensive multi-step
methods.
Exemplary embodiments of the invention are provided as follows: (1)
A polymeric composition comprising: (a) a first ethylene copolymer
having: i. an E.sub.A in the range from greater than or equal to 35
to less than or equal to 60; and ii. a Mw.sub.A of less than
130,000; and (b) a second ethylene copolymer having: i. an E.sub.B
in the range from greater than or equal to 35 to less than or equal
to 85; and ii. a Mw.sub.B of less than 70,000. (2) The polymeric
composition of embodiment (1), wherein the first ethylene copolymer
and/or the second ethylene copolymer have a substantially linear
structure. (3) The polymeric composition of embodiment (1) or (2),
wherein the first ethylene copolymer and/or the second ethylene
copolymer have a MWD of about 2.4 or less. (4) The polymeric
composition of any one of embodiments (1)-(3), wherein the MWD of
the first ethylene copolymer is in the range from greater than or
equal to 1.80 to less than or equal to 1.95, and/or wherein the MWD
of the second ethylene copolymer is in the range from greater than
or equal to 1.80 to less than or equal to 1.95. (5) The polymeric
composition of any one of embodiments (1)-(4), wherein E.sub.A is
less than E.sub.B for the polymeric composition, and/or wherein the
difference between E.sub.B and E.sub.A is greater than or equal to
5. (6) The polymeric composition of any one of embodiments (1)-(5),
wherein MI.sub.A/MI.sub.B is less than or equal to 3.0 for the
polymeric composition. (7) The polymeric composition of any one of
embodiments (1)-(6), wherein the weight percent of the first
ethylene copolymer in the polymeric composition is greater than the
weight percent of the second ethylene copolymer in the polymeric
composition. (8) The polymeric composition of any one of
embodiments (1)-(7), wherein the Mw.sub.A is less than 90,000
and/or the Mw.sub.B is less than 60,000. (9) The polymeric
composition of any one of embodiments (1)-(8), wherein the first
and/or second ethylene copolymers comprises ethylene and a
comonomer selected from the group consisting of propylene, butene,
hexene, octene, and mixtures thereof. (10) The polymeric
composition of embodiment (9), wherein the comonomer of the first
and/or the second ethylene copolymers further comprises a polyene
monomer, and the polymeric composition further comprises up to 5
mole % polyene-derived units. (11) A lubrication oil composition
comprising: (a) a lubrication oil basestock, and (b) the polymeric
composition of any one of the preceding embodiments. (12) The
lubrication oil composition of embodiment (11) having at least one
of: (a) a TE of greater than or equal to 1.5; (b) a SSI of less
than 55; and (c) a complex viscosity at -31.degree. C. of less than
or equal to 500 cSt. (13) A process for making a polymeric
composition comprising the steps of: (a) copolymerizing ethylene
and a first comonomer component in the presence of a first
metallocene catalyst in a first polymerization reaction zone under
first polymerization conditions to produce a first effluent
comprising the first ethylene copolymer of any one of the preceding
embodiments; (b) copolymerizing ethylene and a second comonomer
component in the presence of a second metallocene catalyst in a
second polymerization reaction zone under second polymerization
conditions to produce a second effluent comprising the second
ethylene copolymer of any one of the preceding embodiments; and (c)
forming the polymeric composition of any one of the preceding
embodiments, wherein the first and second polymerization conditions
are independently selected from the group consisting of slurry
phase, solution phase and bulk phase; and wherein the first and
second polymerization reaction zones are in series, in parallel or
the same. (14) A polymeric composition comprising: (a) a first
ethylene copolymer having: i. an H.sub.A in the range from greater
than or equal to 0 to less than or equal to 30; and ii. a Mw.sub.A
of less than 130,000; and (b) a second ethylene copolymer having:
i. an H.sub.B in the range from greater than 30 to less than or
equal to 60; and ii. a Mw.sub.B of less than 70,000. (15) The
polymeric composition of embodiment (14), wherein the first
ethylene copolymer and/or the second ethylene copolymer have a
substantially linear structure. (16) The polymeric composition of
embodiment (14) or (15), wherein the first ethylene copolymer
and/or the second ethylene copolymer have a MWD of about 2.4 or
less. (17) The polymeric composition of any one of embodiments
(14)-(16), wherein MWD of the first ethylene copolymer is in the
range from greater than or equal to 1.80 to less than or equal to
1.95, and/or wherein MWD of the second ethylene copolymer is in the
range from greater than or equal to 1.80 to less than or equal to
1.95. (18) The polymeric composition of any one of embodiments
(14)-(17), wherein H.sub.A is less than H.sub.B for the polymeric
composition. (19) The polymeric composition of any one of
embodiments (14)-(18), wherein H.sub.A is in the range from greater
than or equal to 0 to less than or equal to 10. (20) The polymeric
composition of any one of embodiments (14)-(19), wherein
MI.sub.A/MI.sub.B is less than or equal to 3.0. (21) The polymeric
composition of any one of embodiments (14)-(20), wherein the weight
percent of the first ethylene copolymer in the polymeric
composition is greater than the weight percent of the second
ethylene copolymer in the polymeric composition. (22) The polymeric
composition of any one of embodiments (14)-(21), wherein the
Mw.sub.A is less than 90,000 and/or the Mw.sub.B is less than
60,000. (23) The polymeric composition of any one of embodiments
(14)-(22), wherein the first and/or second ethylene copolymers
comprises ethylene and a comonomer selected from the group
consisting of propylene, butene, hexene, octene, and mixtures
thereof. (24) A lubrication oil composition comprising: (a) a
lubrication oil basestock; and (b) the polymeric composition of any
one of embodiments (14)-(23). (25) A process for making a polymeric
composition comprising the steps of: (a) copolymerizing ethylene
and a first comonomer component in the presence of a first
metallocene catalyst in a first polymerization reaction zone under
first polymerization conditions to produce a first effluent
comprising the first ethylene copolymer of any one of embodiments
(14)-(23); (b) copolymerizing ethylene and a second comonomer
component in the presence of a second metallocene catalyst in a
second polymerization reaction zone under second polymerization
conditions to produce a second effluent comprising the second
ethylene copolymer of any one of embodiments (14)-(23); and (c)
forming the polymeric composition of any one of embodiments
(14)-(23), wherein the first and second polymerization conditions
are independently selected from the group consisting of slurry
phase, solution phase and bulk phase; and wherein the first and
second polymerization reaction zones are in series, in parallel or
the same.
When numerical lower limits and numerical upper limits are listed
herein, ranges from any lower limit to any upper limit are
contemplated.
All references, patents and documents described herein are
incorporated by reference herein, including any priority documents
and/or testing procedures to the extent they are not inconsistent
with this text. As is apparent from the foregoing general
description and the specific embodiments, while forms of the
invention have been illustrated and described, various
modifications can be made without departing from the spirit and
scope of the invention. Accordingly, it is not intended that the
invention be limited thereby.
* * * * *